TW200422311A - Use of a copolymer having at least one grafted alkoxy or hydroxy polyalkylene glycol function, as agent improving the activation of the optical brightening and products obtained - Google Patents

Abstract

The invention relates to the use of a water soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer, as agent to improve the activation of the optical brightening of the end product, in the fields of paper, textile, detergents and paint.

Description

200422311 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to the technical field of paper, textiles, detergents and pigments', and especially to the field of fillers and paper coating pigments, which focuses on improving the end product level Optical brightening activation. The invention first relates to a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted on at least one ethylenically unsaturated monomer as an agent for improving the optical whitening activation effect of the final product. use. The invention also relates to an agent for improving the optical whitening activation of the final product. The invention also relates to a water-soluble copolymer having at least one alkoxy group or via a polyalkylene glycol function grafted onto at least one ethylenically unsaturated monomer as a design to improve the optical whitening activation of the final product In addition, it is used as a reagent for a method for dispersing a pigment and / or a mineral filler in an aqueous suspension. It is also about carrying out the dispersion method of the copolymer and the aqueous suspension thus obtained. The invention also relates to the use of the aqueous suspension for the manufacture of fillers and / or coating pigments. It is also about the coating pigments and fillers thus obtained. Finally, it relates to the use of the filler and the coating colorant in the manufacture and / or coating of paper stock. It is also about the paper stock thus obtained. The present invention also relates to a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol s capable of grafting to at least one ethylenically unsaturated monomer as an improved end product optical whitening activation and is implemented in Use of abrasive fillers and / or mineral pigments in aqueous suspensions. It is also related to the grinding method applied to the copolymer and the aqueous suspension thus obtained. 200422311 It also relates to the use of the aqueous suspension for the manufacture of fillers and / or coating pigments. It is also related to coating pigments and fillers thus obtained. Finally, it relates to the use of the filler and the paint colorant for manufacturing and / or coating paper. It is also about the paper stock thus obtained. The invention also relates to a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted on at least one ethylenically unsaturated monomer as an improved final product for optical whitening activation and is implemented in Use of reagents in filler manufacturing methods. It also relates to a method for manufacturing a filler for implementing the copolymer and a filler thus obtained. It is also about the use of the filler for the manufacture of coating pigments. Finally, it is about the paper stock thus obtained. The invention also relates to a water-soluble copolymer having at least one alkoxy or hydroxy polyalkylene glycol function grafted on at least one ethylenically unsaturated monomer as an improved final product for optical whitening activation and is implemented in Reagent use in paint color manufacturing method. It also relates to a method for manufacturing a coating color of the copolymer and a coating color thus obtained. It is also about the use of the coating pigment for coating paper. Finally, it is about the paper stock thus obtained. Furthermore, the present invention relates to the use of the water-soluble copolymer according to the present invention as an additive for manufacturing a suspension of a mineral substance dispersed and / or ground beforehand. It also concerns the use of the suspension thus obtained in the manufacture of paper coating pigments. Finally, the invention relates to the use of the water-soluble copolymer according to the invention as an additive to improve the optical whitening activation in textiles, detergents or pigment compositions, and to the composition of textiles, detergents or pigments containing the additives Thing. 200422311 " Hai paper manufacturing method includes several stages, including: turning pigments and / or mineral fillers into pulp; using the suspension or slurry to make fillers and / or k colorants' using the coating colorant And fillers to manufacture and / or coat paper stock. Through this method, those skilled in the art will remember that it is necessary to obtain a strong activation that can produce light to white, and therefore to obtain a color as white as possible. The increase in whiteness of the final product is a matter of paper manufacturers. The main considerations, The properties of activating the optical whitening effect and the methods to enhance the above-mentioned methods: the known methods of whitening during the process are described in the following through the files that can be found by those skilled in the art in advance. During the Hai method, mineral fillers and / or pigments, such as: carbonic acid, dolomite, kaolin, slip ... paste, titanium oxide, wrought or alumina, are initially slurried alone or as a mixture. For this purpose, a dispersion and / or grinding aid of ore: and 'or mineral fillers is used, which is still referred to as a continuation substance. Although "the mineral substances mentioned by me, = and / or pigments" are used in the description, these terms have the same knife and / or grinding aids for the applicant of this patent. To make the suspension fluid fluid < mechanical action feeder, # by using the abrasive assisted grinding 4 its sleeve Du Wanyoubeixian. Additives can also be used to check the viscosity of the mineral substance suspension in 5 weeks. [Prior art] Therefore, those skilled in the art know how to use text to express _ t EP 0 61 0 534, its description ^ by / Copolymerization of early and non-protonic and protonic acid esters, and protons, and functionalization using difluorene 200422311 polyalkylene monoalkylamines or ethers to prepare polymers. This reagent is especially useful for grinding organic pigments Those skilled in the art also know document WO 00 / 77〇58, which describes copolymers based on mono- or mono-carboxylic Western unsaturated derivatives, copolymers of unsaturated derivatives of polyalkylene glycols, Copolymers of unsaturated polysiloxane compounds or unsaturated vinegar. These copolymers are used as dispersants in suspensions of mineral fillers, which is noteworthy in the cement industry. Those skilled in the art also know document wo 01 / 96007, which describes an ionic, water-soluble silk material that has a fluorenyl or fluorinated polyalkylene glycol function, and its role is to disperse and / or assist the grinding of pigments and / or mineral fillers. Free, ^ The artist will know the file FR 2 7 7 182, which explains how to polymerize suspensions of inorganic pigments using polymers based on polypropylene salts and phosphonates. However, neither these documents nor other documents appearing in prior art teaches oxyhydroxide or tritium The grafting of the poly (ethylene glycol) glycol group can improve the activation of optical whitening. 'The aqueous suspension of the pigment and / or mineral filler then enters the composition of the filler and / or paint colorant. In the filler In the case, the filler is added to the fiber before the paper is manufactured; what I call the filler # added to the mass or the filler during the fiber suspension # solution fed to the paper machine is like As indicated in the document Shame 99/42657. The filler can be added to the fiber in the form of a suspension of pigments and / or mineral fillers. Optical brighteners can also be added to the theory: Hiroji's later substance was "added To cleaners or to use, a, or paper to improve its whiteness "fluorescent materials (" Science Word Oxford University Publishing, Market House Bookstore, 1999 "), this B degree is for end use Basic Importance. A homogeneous styrenic molecule with an optical brightener, which has the property of absorbing part of the wavelength of μ wavelengths, so that it can be re-emitted in the visible spectrum, so that the whiteness of the product can be improved. This white The degree is characterized by the similar nanometer wavelength = paper diffusion reflection coefficient, measured with and without UV, marked 57 and Re7, respectively, and then can calculate the difference Δϋν = 1? Chuan · —D57_. These coefficients are Measured in accordance with the French standard NF Q 03-039 using a spectral colorimeter that conforms to the specifications of the experimental port 2 Cai Q 〇3-〇38. The whiteness can also be measured by the coefficient w according to the standard IS0 / FDIS 1 1475 (c⑻ for feature identification.) In the case of paint colorants, the paint colorants are especially used by adding a certain amount = additive to an aqueous suspension of pigments and / or mineral fillers. Latex and optical brightener as a binder. Most: Chemicals known as "carriers" or "activators" of optical brighteners can be added to these substances, meaning that it can make the brightener active, thereby improving the whiteness of the final product. . In this way, in order to activate optical whitening, a well-known method is to incorporate certain compounds into paper coating pigments, such as polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) ), Polyvinylpyrrolidine 5) Lumin or Dianfen 'These are described in the document "Glass of Light Coated with White Paper" (Allg · Papier-Rundschau, November 5, 1982 200422311' No. 44 'P. 1242). Similarly, the document "Effects of Polyethylene Glycol on the Properties and Coating Quality of Paint Colorants" (wochbi.

Papierfabr, February 15, 1978, Volume 206, Number 3, pp. 109-112) teaches those skilled in the art how to use polyethylene glycol as a carrier for optical whitening in paper coating pigments. Those skilled in the art also know document JP 60 1 34096, which explains how to use latex binders, fillers such as calcium carbonate, chalk, talc, kaolin, or stilbene containing acrylic or styrene-butadiene copolymers as the base. Ethylene-based or polyethylene glycol compounds are used to coat paper. This will increase the whiteness of the paper stock. Finally, those skilled in the art know the document Ep 丨 〇 \\ 083 ', which describes a polymer composition containing at least one polyethylene and i less than one water-soluble polymer neutral or alkaline pH, which is used in Paper coating pigments to improve water retention and activate optical whitening of the final product. The applicant pursued his research from the viewpoint of improving the optical whitening activation of the paper. M was also surprised to find that in the pigment and / or mineral filler grinding method, pigment and / or mineral filler dispersion method, filler manufacturing method, In the coating pigment manufacturing method, 'the use of a water-soluble copolymer having at least one grafted silk-based or silk-polymerized diol functionality on at least one ethylenically unsaturated monomer' can make it possible to improve the paper Optical whitening activation to improve the whiteness of the final product. [Summary of the Invention] In this way, the use of the water-soluble copolymer according to the present invention as an optical whitening activator is characterized in that the copolymer has at least one alkoxy group or is functionally grafted to At least _ dilute bond unsaturated mono-J carcass. More specifically, the presence of a monomer of formula (I) The present inventors have found that at least one

(I) where m and P represent the number of oxyalkylene units, which is less than or equal to 150, the number of ethylene oxide units, which is less than or equal to 150, q which is equal to at least 1, and such that 5 < (m + n + p) qSl50 The integer-Ri represents hydrogen or methyl or ethyl-h represents hydrogen or methyl or ethyl R represents a group containing a polymerizable unsaturated function, and preferably belongs to the vinyl group and acrylic, methacrylic, cis -A group of butenedioic acid, fen ..., crotonic acid, and vinyl glutamate, and aminomethyl ethyl acetic acid unsaturated compounds such as ethyl acrylamidoacetate, methacrylamidoic acid _ The group of α-methyl-isopropyl-benzylaminocarboxylic acid and allyl ethyl methanoate, and the group of substituted or unsubstituted allyl or vinyl ether Groups, or groups of ethylenically unsaturated fluorenes or fluorimines, represent gas or nicotinic groups having 1 to 40 carbon atoms, making it possible to develop polyalkylenes having at least one alkoxy or hydroxy group 12 200422311 A copolymer of soil grafts grafted onto at least one ethylenically unsaturated monomer, thereby improving the optical properties of the paper stock. White activation. & Because: According to the present invention, the water-soluble copolymer comprises: ^ anionic monomers having diene or dicarboxylic acid or phosphoric acid or phosphonic acid or sulfonic acid functions or a mixture thereof, b) at least one non-ionic monomer The non-ionic single system is composed of at least one monomer of formula 或 or a mixture of several monomers of formula ：:

Where m ϋ P represents the number of alkylene oxide units, which is less than or equal to 丨 5〇-η represents the number of ethylene oxide units, which is less than or equal to 150, q represents equal to at least 1 and makes 5 < (m + n + p) q < 150, and preferably an integer of 15 $ (m + n + p), 12 Ri, one Ri represents hydrogen or fluorenyl or ethyl, one h represents hydrogen or fluorenyl or ethyl,-R represents one Polymerizable unsaturated functional groups, which preferentially belong to the ethylene group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl phthalate, and amino groups Ethyl formate unsaturates such as ethyl acrylaminoformate, ethyl acrylamino amidinoacetate, α-α'diamidyl-isopropenyl-benzylamino ethyl amidate and allyl 13 200422311 Groups in the Tokaido text, and groups of substituted or unsubstituted dilute propyl or & diyl_1, or groups of ethylenically unsaturated amidines or amines -R 'represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents 1 to 4 carbon atoms. Hydrocarbyl, c) if possible, at least one monomer or derivative thereof in the form of acrylamide or methacrylamide, such as N_ [3- (dimethylamino) propyl] acrylamide or N [3 -(Monomethylamino) propyl] methacrylamide and mixtures thereof, or at least one water-insoluble monomer such as alkyl acrylate or alkyl methacrylate, unsaturated esters such as N-methacrylic acid N- [2- (dimethylamino) ethyl] ester or acrylic acid N- [2- (dimethylamino) ethyl] ester, ethyl alcohols such as vinyl acetate, vinyl D-biolone , Styrene, a-methylphenethylhydrazone and its derivatives, or at least one cationic monomer or quaternary ammonium, such as gasification or sulfuric acid [2-((methacryl) oxy) ethyl] trimethylammonium , Chlorinated or sulfuric acid [2- (propenyloxy) ethyl] dimethyl], chlorinated or sulfuric acid [3- (propenylamino) propyl] trimethylammonium, gasified or disulfuric acid Methyl diallyl ammonium, gasified or [3-mono (methacrylamido) propyl] trimethylammonium sulfate, or at least one organic fluorinated or organosilicated monomer, or several of these monomers Body mixtures, d) if possible, At least one monomer having at least two ethylenically unsaturated material having, in the remainder of the present application is called a crosslinking monomer, components a), b), c) and d) is equal to the sum of the proportion 1〇〇%. The copolymer produces an improvement in the optical whitening activation of the paper stock. This goal is achieved thanks to the use of a water-soluble copolymer 200422311 containing the following components: (a) at least one ethylenically unsaturated monofunctional or dicarboxylic acid or sulfonic acid or phosphoric acid or phosphonic acid or linolenic acid function Anionic monomers or mixtures thereof, (b) at least one non-ionic monomer of formula (I), (c) if possible, at least one monomer or derivative thereof in the form of acrylamide or amidinoacrylamide, such as N -[3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamine and mixtures thereof, or at least one water-insoluble monomer , Such as alkyl acrylate or methacrylate, unsaturated vinegars such as N- [2- (dimethylamino) ethyl] methacrylate or N- [2- (dimethylamine methacrylate) (Ethyl) ethyl] esters, vinyls such as vinyl acetate, vinylpyrrolidone, styrene, α-methylstyrene and derivatives thereof, or at least one cationic monomer or quaternary ammonium, such as gasification or sulfuric acid [2_ (Methacryloxy) ethyl] trimethylammonium, chlorinated or sulfuric acid [2 — (propylenepropoxy) ethyl] trimethylammonium, gasified or sulfuric acid [3 (Acrylamino) propyl] trimethylammonium, vaporized or diamidyldiallylammonium sulfate, vaporized or sulfuric acid [3-((Methylacrylamido) propyl) propyl] trimethyl , Or at least one organic fluorinated or organosilicated monomer, or a mixture of several of these monomers, (d) if possible, at least one cross-linking monomer, components a), b), c) and d) The sum of the proportions is equal to 100%. According to the present invention, the use of a water-soluble copolymer having at least one alkoxy group or grafted with at least one ethylenically unsaturated monomer via a polyalkylene glycol functional group, resulting in improved optical whitening activation of the paper stock, It is characterized in that the water-soluble copolymer is composed of at least one ethylenically unsaturated anionic monomer having a monocarboxylic acid function 15 200422311 'It is selected from a group having a monocarboxylic acid function such as acrylic acid or methacrylic acid or two The carboxylic acid hemi-S is intended to be cis-butenedioic acid or an ethylenically unsaturated monomer which decomposes Ci to c4 monoester of aconitic acid, or a mixture thereof, or is selected from the group having dicarboxylic acid functions such as crocid acid, isocroton Acid, cinnamic acid, decomposed aconitic acid, maleic acid, or pelvic anhydride, such as ethylenically unsaturated monomers of maleic anhydride, or selected from sulfonic acid functions such as acrylamino-methyl -Propane-sulfonic acid, ethylenically unsaturated monomers of sodium methallyl luteinate, ethylene sulfonic acid and styrene sulfonic acid, or selected from the group consisting of phosphonic acid functions such as vinyl phosphoric acid and ethylene methacrylate Esters, propylene methacrylate, propylene Ethylenically unsaturated monomers of ethylene phosphate, propylene phosphate acrylic acid, and ethoxylates thereof, or selected from ethylenically unsaturated monomers having a scaly acid function such as vinylphosphonic acid, or a mixture thereof, b) at least one nonionic ethylenically unsaturated monomer of formula (1):

One claw and P represent the number of alkylene oxide units, which is less than or equal to 15〇η represents the number of ethylene oxide units, which is less than or equal to ι50. -Q represents equal to at least 1 and such that, and preferably such that n + p) an integer of q212〇, one Ri represents hydrogen or methyl or ethyl, 16 200422311-R2 represents hydrogen or fluorenyl or ethyl, and-R represents a group containing a polymerizable unsaturated functional group, preferably ethylene Base groups and groups of acrylic acid, methacrylic acid, cis-butenedioic acid, decomposed aconitic acid, crotonic acid, and vinyl esters, and ethyl urethane unsaturated compounds such as acrylic amino Ethyl acetate, the group of ethyl methacrylamidoacetate, α-α'dimethyl-isopropylamidino-benzylaminoformate, and ethyl allylaminoacetate, and A group of substituted or unsubstituted allyl or vinyl ethers, or a group of ethylenically unsaturated fluorenes or fluorimines,-R 'represents hydrogen or a group having 1 to 40 carbon atoms Hydrocarbyl group, and preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 4 carbon atoms, or several formulae I) a mixture of monomers, c) if possible, at least one acrylamide or methacrylamide monomer or derivative thereof, such as N_ [3- (dimethylamino) propyl] acrylamide Or N- [3- (dimethylamino) propyl] methacrylamidine and mixtures thereof, or at least one water-insoluble monomer, such as alkyl acrylate or alkyl methacrylate, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate or N- [2- (dimethylamino) ethyl] acrylate, vinyls such as ethyl acetate, vinyl Pyrrolidone, styrene, α-methylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium, such as gasification or sulfuric acid [2- (methacryloxy) ethyl] trimethyl Ammonium, chlorinated, or sulfuric acid [2- (propenyloxy) ethyl] trimethylammonium, vaporized or sulfuric acid [3- (acrylamino) propyl] trimethylammonium vaporized or dimethyl sulfate Diallyl ammonium, gasification or sulfuric acid [3-mono (methyl 17 200422311 acrylamido) propyl] trimethyl ammonium, or at least one organic fluorinated or organolitholated monomer 'has priority From the formula Molecular IIa) or Formula (Nb), and the formula (Ila) molecule is

Where-ml, pi, m2, and p2 represent the number of alkylene oxide units, which is less than or equal to 150-nl and n2 represent the number of ethylene oxide units, which are less than or equal to 150, Q1 and Q2 represent at least equal to 1, and make 0 < ( ml + nl + pl) qlsi50 and an integer of 0s (m2 + n2 + p2) q2d50, -r represents a number that is made, -R3 represents a group containing a polymerizable unsaturated functional group, which preferentially belongs to the vinyl group and acrylic acid , Methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl phthalates, and amino ethyl acetate unsaturated compounds such as ethyl acrylamino ethyl acetate, methyl A group of ethyl acrylaminoformate, α-α-amyl-isopropenyl-benzylaminoacetic acid ethyl and allyl acrylamine ethyl alcohol, and substituted or unsubstituted Groups of dilute propyl or vinyl ethers, or groups of ethylenically unsaturated fluorenes or fluorimines, h N R5, R10 and R11 represent hydrogen or methyl or ethyl,

Re, R ?, Rs, and R9 represent a straight 18 200422311 chain or branched alkyl group, aryl group, and I with 20 to 20 carbon atoms. In the case of a square group or an aralkyl group, or a mixture thereof, R12 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and A and B are groups that may exist, in this case, it represents 1 to 4 carbons. Atomic nicotinic group, the formula (lib) is R-A-Si (〇B) 3 where one R represents a group containing a polymerizable unsaturated function, which preferably belongs to the vinyl group and acrylic, fluorenyl acrylic, The group of butenedioic acid, decomposed aconitic acid, crotonic acid, and vinyl peptidate, and ethyl urethane unsaturated compounds such as ethyl acrylaminoacetate, ethyl methacrylic acid ethyl ester, -α'difluorenyl-isopropyl-benzyl urethane and allyl urethane groups, and substituted or unsubstituted allyl or ethyl groups Group, or a group of ethylenically unsaturated amidines or amines, where A is a possible group, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms, and β represents a group having A hydrocarbon group of 1 to 4 carbon atoms, or a mixture of several of these monomers, d) if possible, at least one crosslinked precursor It is selected from (but not completely) diethylene glycol acrylate, trihydroxypropane triacrylate, allyl acrylate, allyl cis-butenedioate, methylene-bis-acrylamide , Fluorenyl-bis-fluorenylpropenamide, tetraallyloxyethane, triallyl cyanurate, prepared from polyhydric alcohols such as neopentaerythritol, sorbitol, sucrose or others19 Allyl ethers, groups, or molecules selected from formula (ΠI):

Where (III) p4 represents the number of alkylene oxide units, which is less than or equal to one m3, p3, m4, and less than 150, .. the number of gasification ethylene units, which is less than or equal to 150, one, and Q4. (^ m3 + n3 + p3) q3q5Qi is at least equal to 1 and such that 'k (m4 + n4 + p4) q4U50 is an integer, Γ represents a number such that 1々, $ 200, and η and η 4 -Rn represent an aggregate Unsaturated functional groups, which preferentially belong to the ethylene group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconite @ 文 巴豆 驮, and vinyl peptidate, and ethyl carbamate Ester unsaturated compounds such as ethyl acryl urethane, methacryl urethane, α-α 'dimethyl-isopropenyl-benzyl urethane and allyl ethyl methacrylate Groups, and groups of substituted or unsubstituted allyl or ethyl groups, or groups of unsaturated unsaturated amines or amines-R14, R] 5, R20 and R2I represents hydrogen or methyl or ethyl,-R16, Rn, Ri8, and represents a straight or branched alkyl, aryl, aryl, or aralkyl group having 1 to 20 carbon atoms, or Compound 20 200422311 -D and E are possible groups. In this case, they represent a hydrocarbon group having 1 to 4 carbon atoms, or a mixture of several of these monomers. Ingredients a), b), c) The sum of the proportions of d) is 100%. More specifically, the use of the above-mentioned copolymer is characterized in that the water-soluble copolymer is composed of the following, expressed by weight: a) at least one of 2% to 95%, and more particularly 5% to 90% A monoweilenic acid-functional ethylenically unsaturated anionic monomer, which is selected from the group consisting of C with monotarctic acid functions such as acrylic acid or fluorenyl acrylic acid or dibasic acid half esters such as maleic acid or decomposing aconitic acid. C4 monoester ethylenically unsaturated monomers, or mixtures thereof, or selected from dicarboxylic acid functions such as crotonic acid, isocrotonic acid, cinnamic acid, decomposed aconitic acid, cis-butenedioic acid, or carboxylic acid anhydrides such as An ethylenically unsaturated monomer of cis-butadiene anhydride, or selected from the group consisting of sulfonic acid functions such as acrylamino-methyl-propane-continuous acid, sodium methallyl lutein, ethylene vinyl acid and Ethylenic unsaturated monomers of styrene sulfonic acid, or selected from phosphoric acid functions such as ethylene androsic acid, methyl malonate, and acetic acid methyl ester Ester of ethylenically unsaturated monomers of diester, acrylic acid propylene phosphate and its ethoxylate, or selected from phosphine Functional ethylenically unsaturated monomers such as vinylphosphonic acid, or mixtures thereof, b) 2% to 95%, and more particularly 5% to 90% of at least one nonionic ethylenic formula of formula (I) Unsaturated monomer · 21 200422311

(I) where m and P represent the number of alkylene oxide units, which is less than or equal to 150, 11 represents the number of ethylene oxide units, which is less than or equal to 150, and Q represents at least 1 and such that 5 ^ (m + n + p) q $ 150, and preferably an integer such that 15s (m + n + p) qU20,-Ri represents hydrogen or methyl or ethyl,-h represents hydrogen or methyl or ethyl, and-R represents a Polymerization of unsaturated functional groups, preferably belonging to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and ethylacetic acid, and amino groups Ethyl acetate unsaturates such as ethyl acryl urethane, methyl propyl urethane, α-α 'dimethyl-isopropenyl-benzyl amino acetic acid ethyl ester and allyl acetate A group of feminine ethyl acetate, and a group of substituted or unsubstituted amidyl or vinyl ether, or a group of ethylenically unsaturated amidamines or amidines,-R 'Represents a hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 4 carbon atoms, 22 2004 22311 or a mixture of several monomers of formula (I) 'c) 0% to 50% of at least one monomer or derivative thereof in the form of acrylamide or methacrylamine, such as N- [3- ( Dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamine and mixtures thereof, or at least one water-insoluble monomer, such as alkyl acrylate Or alkyl methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate or N- [2- (dimethylamino) ethyl] acrylate, Ethylenes such as vinyl acetate, vinylpyrrolidone, styrene, α-fluorenylstyrene and their derivatives, or at least one cationic monomer or quaternary amidine, such as gasification or sulfuric acid [2 methacryl (Oxy) ethyl] trimethylammonium, gasified or sulfuric acid [2- — (propenyloxy) ethoxy] ethyl] dimethylammonium, chlorinated or sulfuric acid [3- (propenylamino) propyl] triamidine Ammonium, vaporized or difluorenyl diallyl ammonium sulfate, vaporized or di- (methacrylamido) propyl] trimethylammonium sulfate, or at least one organic fluorinated or organic stone The oxidized monomer 'is preferably selected from Formula (Ila) or Formula (I ib), the molecule of formula (Ila) is >

Rb

Where p2 represents the number of alkylene oxide units, which is less than or equal to-ml, pi, m2, and less than 150, and the number of ethylene units for gasification, which is less than or equal to 15 | 23 200422311 and q2 represent at least equal to 1 and make 0S (ml + nl + pl) qi $ i50 and an integer of 0S (m2 + n2 + p2) q2sl50, -r represents a number that makes Krs200,--3 represents a group containing a polymerizable unsaturated function, Preferentially belongs to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl phthalate, and ethyl amino ethyl ester unsaturated compounds such as allylamine Groups of ethyl carbamate, methacryl urethane, α-α, difluorenyl-isopropenyl-benzylamino carbamate and allyl urethane, and substituted Or an unsubstituted allyl or vinyl group, or a group of dilute unsaturated unsaturated amines or amimines, where R4, R5, R10, and Rn represent hydrogen or methyl or ethyl -R6, R7, R8 and R9 represent a linear or branched alkyl, aryl, alkaryl or aralkyl group having 1 to 20 carbon atoms, A mixture thereof, Ri2 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and groups A and B 疋 may exist. In this case, it represents a hydrocarbon group having 1 to 4 carbon atoms, and the formula (lib) is R-A-Si (〇B) 3 where ~ R represents a group containing a polymerizable unsaturated function, preferably belonging to the vinyl group and acrylic acid, methacrylic acid, maleic acid, decomposed aconitine, croton Group of acids, and vinyl phosphonates, and urethane unsaturated compounds such as acryl urethane, methacryl urethane 24 200422311 ethyl ester, α-α, dimethyl-isopropene Of benzyl-benzyl urethanes and allyl urethanes, as well as groups of substituted or unsubstituted allyl or ethene groups, or dilute unsaturated ethylamines Group A or fluorimine group A is a possible group, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms, B represents a nicotinyl group having 1 to 4 carbon atoms, or a number A mixture of such monomers, d) at least one crosslinking monomer ranging from 0% to 3%, which is selected from (but not completely) Ethylene methacrylate, trihydroxypropane triacrylate, propylene :, allyl maleate, methylene-bis-acrylamide, cadaverine A group consisting of allyloxyethane, triallyl cyanohydrin such as neopentyl alcohol, sorbitol, sucrose, or other airborne propyl ethers, or selected from the group consisting of (Nuclear molecule:

Where (III) one m3 is 150, P4 represents the number of alkylene oxide units, which is less than or equal to one n3 and one Q3 n4 represents the number of ethylene oxide units, and q4 represents at least that it is less than or equal to 150, which is equal to 1 and makes 25 200422311 0s (m3 + n3 + p3) q3sl50 and 〇s (m4 + n4 + p4) q4Sl50,-r 'represents a number such that βγαοο,

-Ri3 represents a group containing a polymerizable unsaturated function, preferably belonging to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl peptidate , And unsaturated urethanes such as acrylaminocarbamate, methacrylaminocarbamate, α-α'dimethyl-isopropenyl-benzylaminocarbamate, and allyl Groups of urethanes, and groups of substituted or unsubstituted allyl or vinyl ethers, or groups of ethylenically unsaturated fluorenes or fluorimines 14, R2Q, and R21 Represents hydrogen or methyl or ethyl, 16 R17, R18, and RI9 represent straight-chain or branched alkyl, aryl, alkaryl, or aralkyl groups having 1 to 20 carbon atoms, or a mixture thereof

-D and E are possible groups, in this case, which represent a hydrocarbon group having 1 to 4 carbon atoms, or a mixture of several of these monomers, components a), b), c) and d) The sum of the proportions is equal to 100%. [Embodiment] The copolymer used according to the present invention is prepared by a known method of free radical copolymerization in a solution, in a direct or inverse phase emulsion, in a suspension or a sediment, in a suitable solvent, Obtained under the conditions of known catalytic systems and transfer agents, or by controlled radical polymerization methods, such as the known method of reverse addition fragment transfer (RAFT), known as atom transfer from \ 26 200422311 radical polymerization (ATRP) method, known as nitrogen oxide-mediated polymerization (NMp), or known as Cobalxime-mediated free radical polymerization. A. Copolymers obtained in acid form and possibly distilled can also be completely or partially neutralized by one or more neutralizers with monovalent or multivalent neutralization functions. For example, for monovalent functions, From basic cations, especially sodium, potassium, lithium, ammonium or primary, secondary or tertiary fatty amines and / or cyclic amines, such as stearylamine, ethanolamines (mono-, di-, triethanolamine ^ , Early- and diethylamine, cyclohexylamine, fluorenylcyclohexylamine, aminomethylpropanol, groups of groups, or, for polyvalent functions, selected from alkaline earth dications, especially It is Zhenhe #, or zinc and trivalent cations, including especially aluminum or some high-valent cations. Each neutralizer is then operated according to the neutralization rate suitable for each valence. ▲ According to another Variation method. The copolymer obtained from the copolymerization reaction can be processed by one or more polar solvents and divided into numbers according to the statistical or dynamic methods known to those skilled in the art, before or after the complete or partial neutralization reaction. Phases, the polar solvents are In the group consisting of water, methanol, ethanol, propanol, isopropanol, butanol, acetone, tetrahydrofuran, or mixtures thereof, then one of the phases is equivalent to the role used according to the present invention to improve the paper This invention also relates to a copolymer of an agent for optical whitening activation. The present invention also relates to a substance having at least one alkoxy group or a functional group that is grafted onto at least one ethylenically unsaturated monomer via a polyalkylene glycol function, Worse, it can improve the optical whitening activation of paper, detergents, textiles and pigments. 27 200422311 Therefore, according to the present invention, the special role of improving the optical whitening activation is that it is the one mentioned above. Water-soluble copolymer. The specific viscosity of the copolymer is indicated by the symbol Ipe and measured in the following manner. A polymer solution is used to obtain an equivalent of 2.5 grams of sodium neutralized dry aggregate and 50 ml of demineralized water. Then, using a capillary viscometer with a Baume constant of 0.000005 in a thermostatically controlled 25QC water bath, we measured a given volume of the above solution containing the copolymer = when Time, and the outflow time of the same volume of demineralized water without the copolymer. Then the specific viscosity can be defined by the following relationship: 7? = Time)-(outflow time of demineralized surface water) Outflow time β Hai Mao, ,, and moss-like and δ are selected in such a way that the outflow time of pure demineralized water is large, and the shift is 60 to 100, thus producing highly accurate specific viscosity measurement results. The invention also relates to a method for carrying out the dispersion of the copolymer. The dispersion method according to the invention is characterized by using the copolymer, and in particular by using the copolymer in an amount of 0.05 to 5% by dry weight relative to the dry weight of the filler and / or pigment, and more particularly It consists in using the copolymer from 0.1% to 3% dry weight relative to the dry weight of the filler and / or pigment. The method for dispersing in an aqueous suspension of a mineral substance according to this description is characterized in that the mineral substance is selected from the group consisting of calcium carbonate, dolomite, kaolin, moonstone gypsum, titanium oxide, satin white or aluminum hydroxide, mica and Mixtures of these fillers, such as talc-calcium carbonate or calcium carbonate-kaolin mixtures, 28 200422311 or a mixture of calcium carbonate and aluminum hydroxide, or a mixture with synthetic or natural fibers, or a common structure of minerals, such as talc-carbon _ Or talc_ titanium dioxide has a common structure, and is more particularly composed of calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk, or a mixture thereof. The present invention also relates to a method for grinding the copolymer. The method of grinding in an aqueous suspension of a mineral substance according to the invention is characterized by the use of the copolymer, and in particular by using the copolymer in an amount of 0.05% to 5% by dry weight relative to the dry weight of the filler and / or pigment And more particularly in that it uses 0.1% to 3% dry weight of the copolymer relative to the dry weight of the filler and / or pigment. The method for grinding in an aqueous suspension of a mineral substance according to the present invention is characterized in that the mineral substance is selected from the group consisting of calcium carbonate, dolomite, kaolin, moonstone β titanium oxide, satin white or aluminum hydroxide, mica and these fillers This compound of rhenium is, for example, a mixture of talc-calcium carbonate or calcium carbonate-kaolin, or a mixture of calcium carbonate and sodium hydroxide, or a mixture with synthetic or natural fibers. The common structure of minerals or mineral shells, such as the talc-carbonate or talc-titanium dioxide common structure ' and more particularly consists of carbonates such as natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof. The present invention also relates to a method for producing a filler for carrying out the copolymer. A filler manufacturing method according to the present invention is characterized by using the copolymer, and particularly by using the copolymer at a concentration of 0.05 to 5% by dry weight of the filler and / or pigment dry weight, and More particularly, the copolymer is used in an amount of from 01% to satoshi's weight relative to the dry weight of the filler and / or pigment. The present invention also relates to a method for manufacturing a coating color material for implementing the copolymer. 29 200422311 A method for producing a coating colorant according to the present invention is characterized by using the copolymerization and especially by using the copolymer in an amount of 0.05% to 5% by dry weight relative to the dry weight of the filler and / or pigment, and more particularly in The copolymer is used in an amount of 0.1% to 3% dry weight relative to the dry weight of the filler and / or pigment. Aqueous suspensions of the copolymers according to the invention which are still referred to as mineral substances are dispersed and / or ground and / or have fillers and / or pigments with additives, characterized in that they contain the copolymer, and in particular that they contain The copolymer is from 0.05% to 5% dry weight based on the total dry weight of fillers and / or pigments, and is more particularly 0.1 to 3% dry relative to the dry weight of fillers and / or pigments. This copolymer is heavy. Daggers are also characterized in that the filler and / or pigment is selected from the group consisting of calcium carbonate, dolomite, kaolin, talc, gypsum, titanium oxide, satin white or aluminum hydroxide, mica and mixtures of these fillers, such as talc- Calcium carbonate or a mixture of calcium carbonate and kaolin, or a mixture of calcium carbonate and aluminum hydroxide, or a mixture of synthetic or natural fibers, or a common structure of minerals such as talc-calcium carbonate or talc-titanium oxide, Or any other fillers and / or pigments and mixtures thereof that are customarily implemented in the paper industry. The car suspension is good. The aqueous suspension of the mineral substance according to the present invention is characterized in that the mineral substance is calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk or a mixture thereof. The filler according to the invention is characterized in that it contains the copolymer, and in particular in that it contains the copolymer in an amount of 0.05% to 5% by dry weight relative to the total dry weight of the filler and / or pigment, and more particularly lies in With respect to the total dry weight of the filler and / or pigment, the copolymer is found to a dry weight of 0.1%. 30 200422311 The coating pigment according to the invention is characterized in that it contains the copolymer, and in particular that it contains the copolymer in an amount of 0.05 to 5% by dry weight relative to the total dry weight of the filler and / or pigment, and More particular is that the copolymer is from 0.1% to 2% dry weight relative to the total dry weight of the filler and / or pigment. The paper stock produced and / or coated according to the invention is characterized in that it comprises the copolymer. The textile composition according to the present invention is characterized in that it contains the copolymer. The detergent composition according to the present invention is characterized in that it contains the copolymer. The pigment composition according to the present invention is characterized in that it contains the copolymer. The scope and benefits of the present invention can be better understood by the following examples which do not have a general nature. Example 1 This example relates to the use of a copolymer according to the invention in a mineral filler separation method. It also relates to the use of the suspension thus obtained in the manufacture of coating pigments', which is used to coat paper. This embodiment is also related to the measurement of the optical whitening and whiteness of the paper thus obtained. More precisely, the objective of this example is to demonstrate that a water-soluble copolymer containing at least one alkoxy group or a polyalkylene glycol functional graft on at least one ethylenically unsaturated monolimb according to the present invention The efficiency of this graft-functional polymer is lacking compared to previous techniques. Among the tests consistent with this example, the first step was to disperse a suspension of mineral matter according to one of the methods familiar to those skilled in the art. 31 200422311 The BrookfieldTM viscosity of suspensions is determined as follows. The Br0kfieldTM viscosity of the suspension was determined using an RVT BrookfieldTM viscometer in an unstirred beaker at a temperature of 23 ° C and a suitable rotating shaft at 10 and 1000 rpm. Take a reading after 1 minute of rotation. This resulted in two BrokfieldTM viscosity measurements, recorded as μm and μm (). Allow this sample to stand in the beaker for eight days and measure the

BrookfieldTM viscosity. This is the introduction of the appropriate shaft of an RVT BrookfieldTM meter into an unstirred beaker at a temperature of 23 ° C and a rotation speed of 10 and 100 Γριη (μ1 () and μ1ϋ ()). . The reading was taken after i minutes of rotation (BrokfieldTM viscosity before stirring). After the beaker was stirred for 5 minutes, the same BrockfieldTM viscosity measurement was performed (BrookfieldTM viscosity after stirring). This suspension is then incorporated into the composition of the paint colorant. In this example, each of the paint colorants was obtained by dividing 10 (parts by weight) of the dry pigment of the calcium carbonate grinding suspension, 15 parts by weight of a styrene-butadiene latex (sold by Dow Chemical Company) (Trade name: DL92〇TM) * i replacement parts of optical brightener (sold by BAYER company, trade name Blancophor PTM) are prepared by combining. The initial viscosity of the paint pigment can be determined by the same method as that applied to the aqueous suspension of minerals. 4 The paint pigment is used to coat the coated paper of the supporting cardboard manufactured by cascades la Rochette. The whiteness characteristics are expressed by the parameters' mV, R457-UV, AUV, and w (CIE), which are respectively equal to 70%. 3 — 7〇 · 〇— 〇 3 32 200422311 and 49.4. A 21x29 7 cm piece of cardboard was used for each coating test, and the specific gravity was 223 μg / m 2, which was coated with the paint pigment to be tested. The coating was carried out using a laboratory coater (sold from Besatoshi Co., Ltd. under the trade name A Mod. KCC 2G2TM) with replaceable rollers. Each sheet of cardboard was therefore coated to 21 g / m² and then in a non-ventilated oven at 50 ° C. (] Dry for 5 minutes. Test 1 This test illustrates the previous technique and implements a suspension of calcium carbonate based on the previous technique of 0.75% dry weight of the copolymer based on the dry weight of the mineral filler, of which 75 The weight% particles have a diameter of less than 1 μm as measured with a S6digraphTM 5100 grain size analyzer, and have a dry content of 72%. The total weight is (by weight) 70% acrylic acid and 30% cis- It is composed of succinic anhydride. It has a specific viscosity of 1-4 and is neutralized by sodium. Test 2 This test illustrates the present invention and implements a measurement of 0.75% dry weight relative to the dry weight of the mineral filler. The copolymer according to the present invention is a suspension of calcium carbonate, in which 75% by weight of the particles have a diameter of less than 1 μηη as measured with a S6digraphTM 5100 grain size analyzer, and have a dry content of 72%. The copolymer has 1 · Specific viscosity of 2 and neutralized with potassium, and it consists of the following: a) 13.5% acrylic acid and 3.5% methacrylic acid b) 83% monomer of formula (I), where: 33 200422311 h represents a hydrogen ruler 2 represents hydrogen, R represents methacrylic The acid group R 'represents a fluorenyl group (m + n + p) q = 45. For Test 1 and Test 2, the dry content of the paint pigment, its pH and Br0kfieldTM. The degree is between 10 and 100 rpm CiL ^ And μ10 ()). Finally, the R457 + uv and R457_uv parameters of the coated paperboard were measured according to the NF Q 03-038 and NF Q 03-039 standards, and then the difference ΔuVsRm + uv-R457_uv was calculated, and w (CIE was also measured according to the ISO / FDIS 11475 standard. )parameter. The results corresponding to Trial 1 and Trial 2 are summarized in Table I.

Table I Test i: Whiteness of 1¾ coated paperboard of colorants / Previous technique / Inventive number NVM (° / 〇) pH Μί〇Μι 〇〇 ^ 457 + UV ^ 457 > UV △ UV (CIE) Prior technique 1 64, 8 8, 1 1780 325 88, 9 83, 7 5, 2 92, 4 The present invention 2 65, 1 8, 1 5360 860 91, 6 82, 9 8, 7 Τ〇3Γ9 Invention of a graft copolymer containing methoxypolyethylene glycol grafted methyl methacrylate functionalities having a molecular weight of 2000, as indicated by the description of monomer b) in Test 2, its use for activation of optical whitening Effect 2 The whiteness of coated paperboard is significantly improved. In addition, it is worth noting that the BrookfieldTM viscosity of the coating pigment 34 200422311 obtained according to the present invention is compatible with general industrial applications. Example 2 This example relates to the use of a copolymer according to the present invention in a mineral filler grinding method. It is also about the use of the suspension thus obtained in the manufacture of a coating color ', which is used for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, the objective of this embodiment is to explain the effect of the ratio of monomer b) on the whiteness of the coated paper. In the experiments in accordance with this example, the first step was to grind a suspension of mineral matter according to the following method. -Using a Dyno-Milin type fixed cylinder grinder with a rotating impeller, the main grinding system is composed of knot-based beads with a diameter between 0.6 mm and 丨 mm. The total volume occupied by the grinding body is 1,000 cubic centimeters, and its weight is 2700 grams. ',-The volume of the grinding chamber is 1,400 cubic centimeters. -The peripheral speed of the grinder is 10 m / s. -The pigment suspension is circulated at a rate of 40 liters / hour. : The outlet of Dyru ^ MiU ^ is connected with a 200 micron class separator, which can be used to separate the grinding suspension from the grinding body. The temperature was maintained at approximately 60 cC during each grinding test. The particle size of this suspension was measured as follows. One hour after the grinding was completed, the particle size of the pigment suspension sample (expressed as the weight of particles less than Um) was measured with a SedigraphTM 5⑽ large grain 200422311 small analyzer and recovered into a beaker. The BrOKfieldTM viscosity of this suspension was measured according to the method described in the Examples. This suspension was then added to the composition of the paint colorant. In this embodiment, each paint colorant is obtained by dissolving 100 parts by weight of the dry pigment of the calcium carbonate grinding suspension, 15 parts by weight of a styrene-butadiene latex (sold by Dow Chemical Company, commercial product The product is named DL92〇TM) and 1 part by weight of an optical brightener (sold by BAYER Corporation under the trade name 2 Blancophor PTM). This coating color is used to coat pre-coated paper. The characteristics of its whiteness are represented by the parameters I? 457 + 1] ν, Ram, MV, and W (CIE), which are respectively equal to 88.4-85.8-2. 6 and 89.5. A 21 x 29.7 cm piece of cardboard was used for each coating test, with a specific gravity of 96 g / m², and was coated with the coating pigment to be tested. This coating was carried out using a laboratory coater with a replaceable roller (sold by EricHSEN Corporation 'under the trade name Mod KCC 202TM). Each piece of cardboard was then coated to 15 g / m² and dried in a non-ventilated oven at $ 5 for 5 minutes. Test 3 This test illustrates the prior art and implements a suspension of calcium carbonate based on a prior art acrylic homopolymer measured at 0.65% dry weight relative to the dry weight of the mineral filler. Before milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. 36 200422311 This homopolymer has a specific viscosity of 0.64 and is neutralized by calcium hydroxide and sodium. Test 4 This test illustrates the present invention and implements a suspension of the copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler measured at 0.65% dry weight. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μπ1 as measured with a SodigraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 1.08 and is neutralized with sodium, and it is composed of: a) 89. 8% acrylic acid and 0.2% methacrylic acid b) 10% monomer of formula (I), Where: h represents hydrogen I represents hydrogen R represents a fluorenyl acrylic group R 'represents a fluorenyl group (m + n + p) q = l13 Test 5 This test illustrates the present invention and implements it with respect to the dry weight of the mineral filler. A suspension of 0.65% dry weight of the copolymer according to the invention to ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.01 and is neutralized with sodium, and its system 37 200422311 consists of the following: a) 79.6% acrylic acid and 0.4% methacrylic acid b) 20% of formula (I) Monomer, where: h represents hydrogen R2 represents hydrogen R represents methyl acrylic acid group R 'represents methyl (m + n + p) q = l13 Test 6 This test illustrates the present invention and implements the The copolymer according to the invention was measured at 0.65% dry weight to grind the suspension of carbonic acid. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a Nao + + 2 ~ measured by a SodigraphTM 5100 grain size analyzer and had a dry content of 76%. This copolymer has a specific viscosity of 1.08 and is used in sodium #. It consists of the following: 'and its a) 69. 5 ° / ◦ acrylic acid and 0.5% methacrylic acid b) 30% of the formula (I) Body, where:

Ri represents hydrogen, h represents hydrogen, R represents a methacrylic group, and R 'represents methyl (m + n + p). 70% dry weight suspension of the copolymer according to the invention to ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μπ] as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.56 and is neutralized with sodium, and it consists of the following: a) 8.5% acrylic acid and 1.5% methacrylic acid b) 90% monomer of formula (I), where: D represents hydrogen, h represents hydrogen, R represents a methacrylic group, and R 'represents a fluorenyl group (m + n + p). % Dry weight of an acrylic homopolymer according to the prior art to grind a suspension of calcium carbonate. Prior to milling, the calcium carbonate suspension contained weight% particles with less diameter = 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 0.64 and is neutralized with calcium hydroxide and sodium. 0 Test 9 This test illustrates the invention and implements the 1% dry weight measured according to the invention relative to the dry weight of the mineral filler 39 200422311. The copolymer is a suspension of ground carbonic acid. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 coffee as measured with a S6digraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 0.64 and is neutralized with sodium, and is composed of: a) 94.5% acrylic acid and 0.5% fluorenyl acrylic acid b) 5% monomer of formula (I), among them:

Ri stands for hydrogen, h stands for hydrogen, R stands for methacrylic group, R 'stands for methyl (m + n + p), q = l13 for all tests 3 to 9' dry matter content of the mineral suspension, its pH value, its The weight percentage of particles smaller than 1 and 2 microns is a characteristic particle size, which has a BrokfieldTM viscosity (μ1 () and μ1ϋ () measured at t = 0 and then at t = 8 days at 10 and 100 rpm. ) Are measured before and after stirring. Finally, the R457 + uv and R45 7-UV parameters of the coated cardboard are measured according to NF Q 03-038 and NF Q 03-039 standards, and then the difference Δυν = Κ457 + υν- R457-uV 'and also determined the w (CIE) parameter according to ISO / FDIS 1 1475 standard. All results equivalent to Test 3 and Test 9 are summarized in Table π. 200422311 1¾ Whiteness W (CIE) 95.5 97.4 98.4 100.2 101.2 95 · 4 98.0 △ UV CS VO VO 00 to 06 ro 00 Os R457 + UV 85 ^ 85.2 1… r " H 00 84.9 85.5 85.4 85.3 R457 + UV 91.4 92.8 L ——— VH ΓΟ Os 93.4 92.8 91.2 93.2 Fun S JL § ^ ^ s Occupy step 蛑 Μίοο 200 700 430 690 340 〇4747 J 450 2110 1170 1660 400 790 Brookfield ™ viscosity (mPa.s) t = before stirring 8 days M-ioo 800 640 1 1_ 2720 1760 2020 510 1110 〇1 3000 1 2510 20400 9560 5000 1210 4440 Brookfield ™ viscosity (mPa.s) at t = 0 Μίοο 200 0 610 410 740 1 ο 220 〇 £ 510 510 350 i 1_ 1710 1080 1880 320 540 Grain size% < 1 μιη 60.5 53.3 i 1_ 60.5 55.5 44.8 61.3 1 58.8!% < 2 μιη L ^ J 85.9 90.1 85.7 76.1 90.4 89.3; ΙΤ Os as as 00 On Os inch 00 Ο ΟΝ inch ON dry matter content (%) 1 75 · 7 1 75.9 76.2 75.3 75.4 75.8] 75.9 J 0.64 1.08 1_ 1.01 1.08 1.56 1 0.64 0.96 Polymer composition 100% AA 89.8% AA 0.2% AMA 10% M MePEG5000 79.6% AA 0.4% AMA 20% M MePEG5000 69.5% AA 0.5% AMA 30% M MePEG5000 8.5% AA 1.5% AMA 90% M Me PEG5000 100% Α 94.5% AA 0.5% AMA 5% M MePEG5000 test Prior art / Invented Prior art Invented 1_ Invented Invented Invented Invented prior Art Invented Number Inch VO Bu 00 Os One inch Outfitting: ^ < w

200422311 Table II shows that the copolymers used in the mineral filler milling method according to the present invention can significantly improve the optical whitening activation of coated paper and significantly improve its whiteness, regardless of the proportion of monomer b), such as test number 4, 5, 6, and 9. Furthermore, these results also demonstrate that the copolymer according to the present invention can obtain a suspension of a mineral filler which can be treated after storage without agitation. Example 3 This example relates to the use of the copolymer of the present invention in a mineral filler grinding method. It is also about the use of the resulting suspension in the manufacture of coating pigments, which are used for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, the goal of this example is to explain the length of the grafted alkoxy polyalkylene glycol chain (ie, monomer b in formula (I)), and a part of (m + n + p) q value) as well. The influence of the chemical nature of the molecules on the polymer grafted to the polymer's main chain. In this example, the first step is to grind the suspension of the mineral substance exactly as described in Example 2. Its particle size and its BrökfieldTM viscosity were measured completely according to the method described in Example 2. This suspension was then added to the composition of a paint colorant formulated exactly as described in Example 2. Finally, the coating colorant was used to coat paper in accordance with the method described in Example 2, and the coating weight was equal to 15 g / m 2. The paper is a pre-coated paper with a specific gravity of 21 x 29.7 and 96 g / m 2. The characteristics of its whiteness are expressed by parameters R457 + uv, R457 ,, Δυν, and W (CIE), which are respectively equal to 88 · 4 _ 85.8-2.6 and 89.5. 42 200422311 Test 10 This test illustrates the prior art and implements a suspension of calcium carbonate based on the prior art acrylic homopolymer of 0.65% dry weight measured relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphn 5100 grain size analyzer and had a dry matter content of 76%. This homopolymer has a specific viscosity of 0.64 and is neutralized by calcium hydroxide and sodium. Test 11 This test illustrates the invention and implements a suspension of a copolymer according to the invention of 0.65% dry weight measured with respect to the dry weight of the mineral filler to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 叩 as measured by a S6digraphT «5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 0.84 and is neutralized with sodium, and it is composed of: a) 18% methacrylic acid b) 82% monomer of formula (I), where: h represents hydrogen Hydrogen R represents a methacrylic group R 'represents a methyl group (m + n + p) q = 8 Test 12 200422311 This test illustrates the present invention and implements 0-65% of the dry weight measured relative to the dry weight of the mineral filler. The copolymer according to the invention is a suspension of ground carbonate. Prior to milling, the suspension of carbonic acid contained 2 Q% by weight of particles having a diameter of less than 2 测定 as measured with a SodigraphTM 5100 grain size analyzer and having a dry content of 76%. The copolymer has a specific viscosity of 0.78 and is neutralized with sodium, and it consists of the following: a) 8.3% propionic acid and 8.7% methylpropionic acid b) 83% of the monomer of formula (I) Body, where: h represents hydrogen R2 represents hydrogen R represents fluorenyl acrylic group R 'represents methyl (m + n + p) q = 17 Test 13 This test illustrates the present invention and is performed relative to the dry weight of the mineral filler. To 0.65% dry weight of the copolymer according to the invention to grind the suspension of carbonate carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 mm as measured with a S6digraPhTM leaky grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 1.47, and is neutralized with sodium, and it is composed of: a) 17% acrylic acid b) 77.6% of formula (I) Monomer, of which: 44 200422311

Ri represents hydrogen, represents hydrogen, R represents fluorenylpropenyl urethane, and is a product of ethylene methacrylate and diisocyanate toluene. R 'represents methyl (m + n + p) q = 113 c) 5. 4% Ethyl Acrylate Test 14 This test illustrates the invention and implements a suspension according to the invention of 0.65% dry weight of the copolymer according to the invention to grind calcium carbonate relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 3.66 and is neutralized with sodium and is composed of: a) 10% methacrylic acid b) 90% monomer of formula (I), where: h represents hydrogen [2 represents hydrogen R represents 3 isopropenyl α, α-dimethylbenzyl urethane groups represent methyl (m + n + p) q = 113 For all tests 10 to 14, mineral matter is suspended The dry content of the liquid is 45 200422311, its pH value, its particle size identified as a weight percentage of particles smaller than 1 and 2 microns, it is measured at t = 0 and then at t = 8 days at 10 and 1000 rpm The viscosity of BrookfieldTM (μιο and μ_) was measured before and after stirring. Finally, the R457 + UV and R457-UV parameters of coated, stainless steel plates were measured according to NF Q 03-038 and NF Q 03-039 standards. , And then calculate the difference Δυν = Κ457 + υν-R457-uv, and also determine the W (CIE) parameter according to the ISO / FDIS 1 1475 standard. All results equivalent to Test 10 and Test 14 are summarized in Table η. 46 200422311 111 嵴 Whiteness 1_________ _ _ — W (CIE) 95.7 110.9 109.5 112.6 109.0 △ UV IT) 'Ο τ-Η 10.6 1-H TH On R457 + UV; 84.9 85.5 85.0 85.0 85.3 1 R457 + UV | 9L4 96.5 95.6 96.1 95.0 1, §1 ^ 1 § 刼 targets £ w Μ ^ ιοο L_________ 130 890 160 280 i 740 〇1 330 1 7540 220 2960 1 Brookfield ™ viscosity (mPa.s) t = 8 days before stirring Μίοο 320 2030 460 0 (N 00 1500 Ο L ^ J 18750 1440 3800 12300 BrookfieldTN ^ i degree (mPa.s) at t = 0 1_ Μίοο 0 290 150 460 Ο 1 400 1 390 300 1630 1 1 grain size 1_% < 1 μιη P; 35.4 32.7 36.9 J 33.5% < 2 μπι 1 60.2 1 60.4 60.5 63.4 60.6; W inch Os 00 00 0 ON cK VO 〇d dry matter content (%) 76.0 75.3 75.9 75.3 75.4 1 0.64 1 0.84 0.78 1.47 3.66 3.66 Composition of polymer 100% AA 18 AM A 82% M MePEG350 8.3% AA 8.7% AMA 83% M MePEG350 ϋ ϋ illil ^ Q 10% AA, 90% IDMBI MePEG5000 Test prior art / present technology present invention present invention present invention Invention number 1 of the invention ο rH ▼ -H < N ro inch vH # 1 ^^^ 1 & Μο ^^^ ί-ΜΟΟΟ1-ο # ^ «^ Ιι® ^^^-: Γ« ι5Μο ^^ νβ: ^ ι ^ * ι5ο ^^^ $ & ^^ νε: ^ ά: ^^ ο§5;} 3% 〒Ια1-03νΜ Is-rto Bismuth ^ jealousy 婶 0 硪 # 屮 Order: Long Phosphorus 09 & 3% Art 窆 ls-rK3ft4 溆 溆 溆 肊 硪 S0LOCO ¥ 屮 Φ: ^ &0; 0SS3CPWH Sliding to disk ¢: 'K: ^ 3V Buried equipment «:' ιτ ^ νν Bu Cun

200422311 Table 111 shows that the copolymers used in the mineral filler grinding method according to the present invention can improve the optical whitening activation and whiteness of coated papers, on the one hand because they contain alkoxy polyalkylene glycol groups The different nature of the monomers ... is, on the other hand, a value of (m + n + p) q between 5 and 150 in the definition of monomer b) as illustrated by formula (I). Moreover, these results also demonstrate that the copolymers according to the invention can obtain suspensions of mineral fillers which are treated after storage without agitation. Example 4 This example relates to the use of the copolymer of the present invention in a mineral filler grinding method. It also relates to the use of the obtained suspension in the manufacture of a coating colorant ’The coating colorant is used for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, the objective of this example is to illustrate the influence of the nature of the monomers selected from the copolymer components 0 and d) according to the invention. In this example, the first step is to grind a suspension of mineral matter exactly as described in Example 2. Its particle size and its Br00kfieldTM viscosity were determined completely according to the method described in Example 2. This suspension was then added to the composition of a paint colorant formulated exactly as described in Example 2. Finally, the coating pigment was applied to paper in accordance with the method described in Example 2. The coating weight was equal to 5 g / m 2. The paper was a pre-coated paper having a specific gravity of 96 g / m 2 at 21 × 29.7 cm. The whiteness characteristics are represented by the parameters R457 + uv, Iα, Δυν, and W (CIE), which are equal to 88 · 4-85 · 8 — 2.6 and 89.5, respectively. Test 15 48 200422311 This test illustrates the prior art and implements a 70% dry weight of a homopolymer of acrylic acid according to the prior art measured relative to the dry weight of the mineral filler to grind a suspension of calcium acid. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. This homopolymer has a specific viscosity of 0.64 and is neutralized by calcium hydroxide and sodium. Test 16 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate with respect to the dry weight of the mineral filler of 0.70% dry weight measured. Prior to milling, the calcium carbonate suspension contained 200 ri / 6 with particles less than 2 in diameter as measured by a S6digraphT «5100 grain size analyzer and had a dry matter content of 76%. And its department

The copolymer has a specific viscosity of 2.74 and is neutralized with sodium and consists of: a) 11 · 8% acrylic acid and 16% methacrylic acid b) 69 · 2% of a monomer of formula (I) Body, where:

Ri represents hydrogen 1? 2 represents hydrogen R represents methacrylic group R 'represents methyl (m + n + p) q = 113 c) 3% monomer of formula (lib), wherein R represents vinyl 49 200422311 B stands for fluorene-based test 17. This test illustrates the invention and implements a suspension of the copolymer according to the invention to grind calcium carbonate relative to the dry weight of the mineral filler of 0.70% measured. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The far copolymer has a specific viscosity of 2. 8 8 and is neutralized with nano, and it is composed of: a) 11. 8% acrylic acid and 16% fluorenyl acrylic acid b) 69 · 2% of formula (I) Monomers, where the heart represents hydrogen R2 represents hydrogen R represents fluorenyl acrylic group R 'represents methyl (m + n + p) q = ll3 c) 3% monomer of formula (lib), where R represents Fluorenyl acrylate A represents propyl chain B represents fluorenyl test 18 This test illustrates the present invention and implements a copolymer according to the present invention to grind carbonic acid in an amount of 0.70% dry weight measured relative to the dry weight of mineral filler Suspension of calcium. Prior to milling, the calcium carbonate suspension contained 2 (%) by weight particles having a diameter of less than 2 μm as determined by a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 3.52 and is neutralized with sodium, and it is composed of: a) 11.8% acrylic acid and 16% methacrylic acid b) 69.2% monomer of formula (I), among them:

D represents hydrogen represents hydrogen, R represents a methacrylic group, R 'represents a fluorenyl group (m + n + p), q = 113 c) 3% of a monomer of formula (lib), wherein R represents a methacrylic group, A represents propyl Base chain B represents fluorenyl

Test 19 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate with a dry weight of 0.70% of the measured dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.99 and is neutralized with sodium, and it is composed of: a) 11 · 8% acrylic acid and 16% methacrylic acid 51 200422311 b) 69.2% monomer of formula (I) Body, where:

Ri represents hydrogen I represents hydrogen R represents a methacrylic group R ′ represents methyl (m + n + p) q = 113 c) 3% of monomers of formula (lib), where

R represents a methacrylic group A represents a propyl chain B represents a methyl test 20 This test illustrates the present invention and implements a copolymer according to the present invention, which is ground at a dry weight of 0.70% of the measured dry weight of the mineral filler. Suspension of calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 所 as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%.

This copolymer has a specific viscosity of 2.74 and consists of the following: K 糸 a) 11 · 8% acrylic acid and 16% methacrylamide B) 69 · 2% monomer of formula (I) , Where: I represents hydrogen, R2 represents hydrogen, R represents a methacrylic group, and R 'represents a fluorenyl group. 52 200422311 (m + n + p) q = 113 c) 3% of two perfluoroalkylethyl groups, including Unit test of 21 fluorine atoms and 10 carbon atoms 21 This test illustrates the present invention and implements a copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler, measured at 70% dry weight. Suspension. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μI as measured with a SedigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 2. 7 8 and is neutralized with sodium, and is composed of the following: a) 11.8% acrylic acid and 16% methacrylic acid b) 68.9% formula ( I) monomers, wherein:

Ri represents hydrogen represents hydrogen R represents fluorenyl acrylic group R ′ represents methyl (m + n + p) q = 113 and 3% of monomers of formula (I), where h represents methyl R2 represents hydrogen R represents 曱The acrylate group R ′ represents butyl (m + n + p) q: 32 53 200422311 d) 0.3% ethylene dimethacrylate. Test 22 This test illustrates the invention and implements a suspension of the copolymer according to the invention to grind calcium carbonate with respect to the dry weight of the mineral filler of 0.70% dry weight measured. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 2.80 and is neutralized with sodium, and it is composed of: a) 11.8% acrylic acid and 16% methacrylic acid b) 68-9% monomer of formula (I), Where: D represents hydrogen, R2 represents hydrogen, R represents a methacrylic group, R 'represents methyl (m + n + p), q = 113, and 3% of the monomer of formula (I), where I? M represents a methyl rule 2 represents 1 R represents fluorenyl acrylic group R 'represents methyl (m + n + p) q = 22 d) 0.3% of monomer of formula (III), wherein Ri3 represents propyl methacrylic group 54 200422311

Rl6, Rl7, ^ 18 and R19 represent the absence of fluorenyl groups D and E. m3 = n3 = ρ3 = m4 = n4 = p4 = 〇r5 = 14 For all tests 15 to 2 2 The dry matter content of the suspension of mineral matter, its pH value, its particle size is exceptionally small at a weight percentage of particles less than 1 and 2 microns, its BrookfieldTM viscosity (μ1 measured at t = 0 and then at t = 8 days at 10 and 100 [pm] () And μπο) were measured before and after stirring. Finally, the r457 + uv and r457_uv parameters of the coated cardboard were measured according to NF Q 03-038 and NF Q 03-039 standards, and then the difference Δυν = ^ 57 + υν R457-UV 'was calculated and also according to ISO / FDIS 1 1475 The w (ciE) parameter is determined as standard. The results of all phases in Test 15 and Test 2 2 are summarized in Table I v 55 200422311 ΛΪ Whiteness W (CIE) m Os 107.1 107.6 g TH 107.3 τ ·· ^ g τ-Η △ UV VO inch ON VO inch 〇 \ 寸 inch ON Jδ 85.0 85.4 85.4 85.2 85.6 85.4 R457 + UV 91.1 94.8 95.0 98.4 94.8 1 Brookfield TI ^ i degree (mPa.s) t = 8 days before stirring m〇0 570 380 420 430 610 0 310 1670 940 1120 1340 1960 j Brookfield ™ viscosity (mPa.s) t = 8 days before stirring ^ 100 360 2030 1340 1850 1430 1900 0 1000 1 16000 8480 13980 8080 14880 i Brookfield ™ viscosity (mPa.s) at t = 0 Hours 100 § 560 320 560 290 680 0 £ 390 1930 810 1890 750 2390 Grain size% < 1 μπι 59.6 45.3 48.3 47.8% < 2 μπι § ON 78.3 75.8 00 80.5 0 ON rn 〇 \ < N ON ο σ; rn On Dry content (%) 76.0 76.5 75.4 VO 75.3 76.2 V 0.64 2.74 2.88 3.52 §; 2.74 Polymer composition 100% AA 11.8% AA 16% AMA 69.2% M MePEG5000 3% 3-vinyltriethoxy Silane 11.8% AA 16% AMA 69.2% M MePEG5000 3% 3-Methacrylfluorenyloxypropyltrimethylsilane. ^ O Vi: — Key wlp. CN Double $ Note ¢-rn 客 m ίο ”1 ^ ί ^ ζ: 4 S —— ^ M rn m Avoid IS § ^ ^ V? S 衾 m Test the prior art / the prior art of the present invention the present invention The invention of the invention The invention of the invention The present invention number v0000 σ \ ISMO Bismuthine ^-馇 ««: 砩 宕 000 000 ^ ^ order: long ^ 000 ^ 〇3% ^ 2 helmet y ^ i: 伥 ^ vwv Outfit: Long < ¥¥ 910

200422311 §5 Whiteness W (CIE) 104.4 106.5 △ UV inch 00 85.4 85.4 R457 + UV 93.8 94.5 Brookfield ™ viscosity (mPa.s) t = 8 days before stirring Μίοο 1020 580 〇 £ 4160 1760 2 ^ S 5 3柘 ^ | W ^ g Wh Jl〇-? V PQ ^ ^ ο 2210 1840 ο 15560 11520! Brookfiel dTM viscosity (mPa.s) when it = o 8 1820 L 570 Ο 3460 1980 grain size% < 1 μπι 49.9 46.5,% < 2 μιη 82.6 78.6 (N On inch dry content (%) 1 1_ 76.3 76.4 〇2.78 2.80 polymer composition! 11.8% AA 16% AMA 68.9% M MePEG5000 3% butoxymethyl Acrylate 160E 160P 1700 0.3% ethylene dimethacrylate ΓΠ ^ 〇J —2 network — equipment — one _ _ φ! ¢-Μ (-2 test the prior art / the present invention the present invention number-^ < so ^ Mussels (qw 荽 bismuth guest Yuyu 4wff ^ I (NI # ^^: long < 00 | > -1 dsl 309IIS shawl 肊 砩-砩 ^ 卜-^ < 0§1 s .. ^ < 3 Submersible ®: ^ < w 卜 ίο

200422311 Table IV shows that the copolymers used in the mineral filler grinding method according to the present invention can improve the optical whitening and whiteness of coated papers because of different monomers or d) of the copolymers according to the present invention. . Moreover, these results also demonstrate that the copolymers according to the present invention can obtain suspensions of mineral fillers which can be treated after undisturbed storage. The Bebe Example relates to the use of the copolymer according to the invention in the mineral filler grinding method. It also relates to the use of the obtained suspension for manufacturing a coating colorant ', which is used for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, the objective of this example is to illustrate the effect of the specific viscosity of the copolymers according to the invention under a fixed monomer composition. In this example, the first step is to grind a suspension of mineral matter exactly as described in Example 2. Its particle size and its BrookfieldTM viscosity were determined completely according to the method described in Example 2. This suspension was then added to the composition of a paint colorant formulated exactly as described in Example 2. Finally, the coating pigment was applied to paper in accordance with the method described in Example 2. The coating weight was equal to 15 g / m². The paper was a pre-coated paper having a specific gravity of 96 g / m 2 at 21 × 29.7 cm. The whiteness characteristics are represented by parameters R457 + uv, R4 57_uv, AUV and W (CIE), which are respectively equal to 88.4-85.8-2. 6 and 89 · 5. For tests 23 to 28, the weight composition according to the invention is fixed and is equal to: a) 18 · 6% acrylic acid and 1.4% methacrylic acid 58 200422311 b) 80 ° / monomer of formula (I), where :

Ri stands for hydrogen I stands for hydrogen R stands for methyl acrylic acid group R 'stands for fluorenyl group (m + n + p) q = l13 Test 23 This test illustrates the present invention and measures it relative to the dry weight of mineral filler A suspension of the copolymer according to the invention of 0.65% dry weight to ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μπι as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer had a specific viscosity of 0.77 and was neutralized with sodium. Test 24 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to ground calcium carbonate to a dry weight of 0.665% dry weight relative to the dry weight of the mineral filler. Before milling ', the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 µm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.0 and is neutralized with nano. Test 2 5 This test illustrates the present invention and applies a copolymer according to the present invention in an amount of 0.65% dry weight relative to the dry weight of the mineral filler to grind a suspension of carbonate. Prior to milling, the carbonic acid # 5 suspension contained 20% by weight of particles having a diameter of less than 2 所 as measured by a S6digraPhTM 5100 grain size analyzer and had a dry content of 76%. The copolymer had a specific viscosity of 0.40 and was neutralized with sodium. Test 26 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler measured at 0.65% dry weight. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer had a specific viscosity of 2.72 and was neutralized with sodium. Test 2 7 This test illustrates the invention and implements a suspension of the copolymer according to the invention to ground calcium carbonate in an amount of 0.65% dry weight relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer had a specific viscosity of 4.79 and was neutralized with sodium. Test 28 This test illustrates the present invention and applies a copolymer according to the present invention to a suspension of rubidium carbonate in an amount of 0.65% dry weight relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 mm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer had a specific viscosity of 7.85 and was neutralized with steel. 200422311 In this example, the copolymer according to the invention as described in tests 23 to 28 is compared with the prior art copolymer described in test 10 of Example 3. For all tests 23 to 28, the dry matter content of the mineral substance suspension, its pH value, its particle size characterized by the weight percentage of particles smaller than 1 and 2 microns, it was at t = 0 and then at t = 8 days at 10 Brookfield viscosity (μ1 () and μΙ () ()) measured at 100 rpm and 100 rpm were measured before and after stirring. Finally, the r4 57 + uv * r457_uv parameter of the coated paperboard was determined according to the NF Q 03_038 and NF Q 03-039 standards, and then the difference Δυν = Κ457_ R457-UV was calculated, and w was also measured according to the ISO / FDIS 1 1475 standard. (CIE) parameters. All results equivalent to Test 2 3 and Test 2 8 are summarized in Table v 200422311 62 AA ^ L: / ¾¾Ankle AMA > 钋: f ^ MMMMepEG5000 > 71 »: 屮 屮 5000s f &» berry 镠-€ Shackles pb® Ni 00 tNJ to 〇 Numbering test The present invention The present invention The present invention The present invention The prior art of the present invention The prior art / The present invention 18.6% AA 1.4% AMA 80% M MePEG5000 100% ΑΑ 丨 Polymer composition 7.85 4.79 2.72 1.40 1.00 1 0.77 1 | 0.64 | f 75.5 54.7 75.4 75.2 75.0 '1 75.5 1 | 76.0 | Dry content (%) v〇vo fo VO 1 v〇k >) D 00 bo VD 52.6 54.7 57.2 1 65.3 j L47 ^ 1 60..2 |% < 2 μιη grain size 27.4 28.9 30.4 37.9 34.4 25.5!% ≪ 1 μιη 380 1270 810 1 270 I Hk s | 6380 I [400 〇Brookfield7 M viscosity (mPa.s) in t = 〇a4 H- * 360 310 160 140 1220 M-ioo 4660 8660 5200 | 1880 | 1 1880 | 1108001 670 — Driving 970 1220 [1150 580 600 ^ 090 320 ^ 100 530 990 990 320 1 ^ 680 ^ 330 i1 Brookfield TM viscosity (mPa.s) t = 8 days after stirring 240 330 ^ 50 ㈣ 1320 ^ 100 97.8 97.3 96.9 96.9 96 7 91.4 R457 + UV whiteness I_________________________ 85.8 85.9 84.8 84.9 84.8 84.9 84.9 R457 + UV h— ^ to HlLi L12 ^ J H- ^ K) 1L8 〇 \ △ UV 1 114.9 | 1 114.9 | 1 112.7 | 丨 113.8 '' 95.7 W (CIE ) ^ v

200422311 Table V shows that the copolymer used in the mineral filler grinding method according to the present invention can improve the optical whitening activation and brightness of coated paper for a wide range of specific viscosity ranging from 0.5 to 8. Moreover, these results also demonstrate that the copolymers according to the present invention can obtain suspensions of mineral fillers which can be treated after storage without agitation. Example 6 This example relates to the use of a copolymer according to the invention in a mineral filler grinding method. It also relates to the use of the resulting suspension in the manufacture of a coating colorant for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, this example is designed to illustrate the effect of the monomer composition of the copolymer according to the present invention on a fixed ratio of 5,000 methacrylic acid 曱 milk-based polyethylene glycol. In this example, the first step is to grind a suspension of mineral matter exactly as described in Example 2. Its particle size and its Br00kfieldt viscosity 70 were all determined according to the method described in Example 2. This suspension was then added to the composition of the paint colorant formulated by Yuan Quan as described in Example 2. Finally, the paint colorant was used in accordance with the method described in Example 2 for coating paper 'with a coating weight equal to i 5 g / m 2. The paper was a pre-coated paper with a specific gravity of 96 g / m 2 at 21 × 29 · 7 cm. The whiteness characteristics are represented by the parameters R457 + uv, Rmuv, AUV and W (CIE), which are respectively equal to 8 hearts 4-85 · 8-2.6 and 89.5. This test illustrates the prior art and implements a suspension of calcium carbonate based on the prior art acrylic homopolymer of 0.65% dry weight measured relative to the dry weight of the mineral filler 63 200422311. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a weight of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry content of 76%. This homopolymer has a specific viscosity of 0.64 and is neutralized by the hydroxide word and sodium. Test 30 This test illustrates the present invention and implements a copolymer according to the present invention at a dry weight of 0.65% of the dry weight of the mineral filler measured to grind a suspension of carbonic acid. Prior to milling, the carbonic acid-containing suspension contained 20% by weight of particles having a diameter of less than 2 mm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.34 and is neutralized with sodium, and it consists of the following: a) 8.6% acrylic acid and 1.4% methylpropionic acid b) 80% formula ( I) monomers, where: h represents hydrogen R2 represents hydrogen R represents a group R 'represents methyl (m + n + p) q = 113 c) 10% acrylamide test 31 This test illustrates the present invention and the relative implementation The copolymer according to the invention was measured at 0.665% dry weight of the mineral filler dry weight 200422311 to grind a suspension of calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μ® as measured with a S6digraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 1.24 and is neutralized with sodium, and it consists of the following: a) 8.6% acrylic acid, 1.4% methacrylic acid, and 10% ethylene methacrylate phosphate Esters b) 80% of monomers of formula (I), wherein:

Ri represents hydrogen, h represents hydrogen, R represents a methacrylic group, and R 'represents a fluorenyl group (m + n + p). 65% dry weight of a copolymer according to the invention in a suspension of ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.24 and is neutralized with sodium, and it consists of the following: a) 8.6% acrylic acid, 1.4% methacrylic acid, and propylene amidaminomethyl Propane sulfonic acid 65 200422311 b) 80% of monomers of formula (I), where: I represents hydrogen h represents hydrogen R represents a methacrylic group R 'represents methyl (m + n + p) q = l13 Experiment 34 The test illustrates the invention and implements a suspension of the copolymer according to the invention of 0.665% dry weight measured relative to the dry weight of the mineral filler to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry content of 76%. The copolymer has a specific viscosity of 1.92 and is neutralized with sodium, and it is composed of: a) 20 ° / ◦methacrylic acid b) 80% monomer of formula (I), where:

Ri represents hydrogen, h represents hydrogen, R represents a methacrylic group, R 'represents methyl (m + n + p), and q = 113. In this example, copolymers and implementations according to the present invention will be described in Experiments 30 to 33. The prior art copolymers described in Experiment 10 of Example 3 were compared. In this example, the 66 200422311 copolymer according to the present invention as described in Test 34 is compared with the prior art copolymer of 5 Erming in Test 2 9 of the present embodiment. In fact, as can be seen in the corresponding numerical table, a comparison is made of polymers which can obtain suspensions of mineral substances of similar particle size. For all tests 30 to 34, the dry matter content of the mineral substance suspension, its pH, its particle size characterized by the weight percentage of particles smaller than 1 and 2 microns, it was at t = 0 and then at t = 8 days at 1 Brookfiel ™ viscosity measured at 〇 and 100 rpm (Pig and both were measured before and after stirring. Finally, K457 + υν of coated cardboard was measured according to NF Q 〇3-038 and NF Q 03-039 standards * R457_uv parameter 'Then calculate the difference AUV = R457 + uv-R4571V, and also determine the W (CIE) parameter according to the 1S0 / FDIS 11475 standard. All results equivalent to test 30 and test 34 are summarized in Table VI 67 200422311 1¾ Whiteness W (CIE) 95.7 114.9 115.6 115.0 111.5 95.2 113.8 △ UV > 〇vd fS 12.5 12 · 2 2 0 vd ro fH R457 + UV 84.9 rH uS 00 84.7 84.8 85.1 85.0 1 85.5 ρM 91.4 97.1 97.2 97.0 97 · 1 91.0 丨 96.8 ^ ^ ^ ^ ^ Mil «婵 Μ * 1〇〇rH 230 280 ο (Τ-Η 330 τ-Η 780 〇 £ 1 330 I 1 390 I 370 1 280 1 350 L410 1 2920 1 1 9 iiil Μίοο 320 1 720 1 —570 — [420J ο 600 1 2040 〇 670 1 2000 1 1320 1 1 1480 1 1 1380 1 1 2700 1 1129001 Brookfield1 M Viscosity (mPa.s) ▲ t = 〇e4 Μίοο 140 0 r- «4 ο § 450 Ο 1 400 1 [J40j 1 260 1 1 300 1 L210J 1 1220 1 Grain size% < 1 μιη P ; ㈣ 1 31.8 1 ㈣ 1 50.0 48.7% < 2 μιη 1 60..2 1 1 62.2 | 1 61.6 1 1 58.7 1 1 58.7 1 1 82.8] 81.2 inch ON 00 ο σ \ ο as 卜 οό * T) ON Q \ 00 Dry content (%) 1 76.0 1 1 75 · 4 1 1 75 · 9 1 1 75.6 1 1 75 · 4 1 75.7 75.8 g. 1 0.64 1 I1 · 34 1 I.1 · 24 1 L1: 38 1 L24 1 1 0.64 1 1.92 Composition of polymer 100% AA 18.6% AA 1.4% AMA 80% M MePEG5000 Test prior art / present invention present invention present invention present invention present invention present invention number ο Τ-Η ΓΠ ( Ν mma 4040 年 硪 ^ &-装 肊 硪 ”Guest 00 Pan 1: Command: ^ < 000S3% WW 180 Hidden Love 肊: ^ < 3V Hi-Irto Substitute OWVPNI Outfit ¢ ^ ¢-: Long ^ ¥ |

200422311 Table VI shows that for a wide variety of monomer compositions and a fixed ratio of 5,000 methacrylic methacrylates, the copolymers used in the mineral filler grinding process according to the present invention can significantly improve coatings Optical whitening activation of paper and its brightness. Moreover, these results also demonstrate that the copolymers according to the present invention can obtain suspensions of mineral fillers which can be treated after storage without agitation. Example 7 This example relates to the use of a copolymer according to the invention in a mineral filler grinding method. It also relates to the use of the resulting suspension in the manufacture of a coating colorant for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. The objective of this example is to explain the effect of the proportion of the copolymer according to the invention and the nature of the neutralization under the HJ definite monomer composition. In this embodiment, the first step is exactly as explained in the implementation of W 2

Method of grinding a suspension of mineral matter. Its particle size and its BrookfieldTM viscosity are determined exactly according to the method described in _2. ㈣ Add this suspension to the composition of a paint colorant formulated exactly as described in Example 2. Finally, the coating pigment was applied to paper in accordance with the method described in Practice 2 with a coating weight equal to 15 g / m2. The paper is a colored paper with a ratio of 21x29.7 cm t 76 g / m 2. The specificity of its whiteness is expressed by the parameters R457 + uv, R457, uv, predicate, and W (CIE), which are respectively equal to 90.9—83 · 8—7 ^ and 1036. For tests 36 to 39 and tests 41 to 44, the composition of the copolymer according to the invention is fixed and expressed in weight as: 69 200422311 a) 11.8% acrylic acid and 16% methacrylic acid 107.22% Monomers of (1), where: I represents hydrogen, h represents hydrogen, R represents a methacrylic group, and represents a methyl group (m + n + p) q = 8. Test 35 This test illustrates the prior art and is performed with respect to a A measured suspension of 0.65% dry weight of an acrylic homopolymer according to the prior art to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. This homopolymer has a specific viscosity of 0.64 when neutralized with sodium. In this test, a system consisting of a molar content of 70% sodium ion and 30% calcium ion was used to neutralize it. Test 3 6 This test illustrates the present invention and implements a suspension of the copolymer according to the invention to ground carbonic acid of about 65.5% dry weight relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μ [η as measured by a SedigraphTM 5100 grain size analyzer and had a dry content of 76%. This copolymer has a specific viscosity of 1.08 when neutralized with nanometers, and this test was completely neutralized with potassium ions. 200422311 Test 37 This test illustrates the invention and implements a suspension of a copolymer according to the invention of 0.65% dry weight measured relative to the dry weight of mineral filler to grind rhenium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry content of 76%. This copolymer has a specific viscosity of 1.08 when neutralized with sodium. In this test, a system consisting of a molar content of 70% sodium ions and 30% calcium ions was used to neutralize it. Test 38 This test illustrates the present invention and implements a suspension of a copolymer according to the invention of 0.665% dry weight measured with respect to the dry weight of the mineral filler to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20 weight. / q has particles with a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and has a dry content of 76%. The copolymer has a specific viscosity of .08 when it is neutralized with sodium. In this test, a system consisting of 50% sodium ions and 50% magnesium ions was used to neutralize the copolymer. Test 39 This test illustrates the invention and implements a suspension of a copolymer according to the invention to ground calcium carbonate to a dry weight of 0.665% dry weight relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 mm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. 200422311 This copolymer has a specific viscosity of 胄 h 08 when neutralized with nanometer. This test unit was neutralized with aminomethylpropanol. Test 4 0 This test illustrates the prior art and implements a suspension of calcium carbonate based on the prior art acrylic homopolymer of 0.65% dry weight measured relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. This homopolymer has a specific viscosity of 0.64 when neutralized with sodium. In this test, a system consisting of a molar content of 70% sodium ion and 30% calcium ion was used to neutralize it. Test 41 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler measured at 0.65% dry weight. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. This copolymer has a specific viscosity of 1.08 when neutralized with sodium, and this test did not neutralize it (all its carboxylic acid functions are still acid). Test 42 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler of 0.65% dry weight measured. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm 72 200422311 as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer had a specific viscosity of 1.08 when neutralized with sodium, and this test was completely neutralized with triethanolamine. Test 4 3 This test illustrates the invention and implements a suspension of a copolymer according to the invention of 0.65% dry weight measured with respect to the dry weight of the mineral filler to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. This copolymer has a specific viscosity of 1.08 when neutralized with sodium. This test was completely neutralized with ammonium ions. Test 4 4 This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate relative to the dry weight of the mineral filler of 0.65% dry weight measured. Prior to milling, the rhenium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer has a specific viscosity of 1.08 when neutralized with sodium. In this test, a total of 50% of the copolymer was neutralized with potassium ions, and 50% of its functionality was still acid. For all tests 35 to 44, the dry matter content of the mineral substance suspension, its pH value, its particle size characterized by the weight percentage of particles smaller than 1 and 2 microns, it was at t = 0 and then at t = 8 days at 1 BrookfieldTM viscosity measured at 〇 and 100 rpm (μ10 were measured before and after stirring 0 73 200422311 Finally, the R457 + UV and UV of coated cardboard were measured according to NF Q 03-038 and NF Q 03-039 standards. The R457-UV parameter is then the nose difference-R457_uv, and the W (CIE) parameter is also determined according to the ISO / FDIS 1 1475 standard. All results corresponding to Test 35 and Test 44 are summarized in Table VII.

74 200422311 11¾ Whiteness W (CIE) 107.7 110.7 111.2 i 111.9 114.5 111.2 113.8 112.0 112.2 112.7 △ UV 8356 i 10.5 10.6 10.8 11.0 10.1 11 · 4 11.3 丨 11.1 11.4 85.4 85.1 85.4 85.2 85.3 85.9 | 84.9 84.7 1-H 00 84.9 R457 + UV 94.0 95.6 96.0 96.0 96.3 95.0 96.2 97.0 j 96.2 96.3 H. Fun ss% 660 ^ ^ 15% ^ μ s 1 beads Μίοο 600 4300 1470 1340 3240 220 780 680 1490 830 Ο 2690 丨 180001 10200 8440 15000 420 1 3480 1 I 2900 5800! 3880 Brookfield ™ viscosity (mPa.s) at t = 0 Μίοο rH 890 560 280 1350 120 410 220 500 270 Ο 310 | 2330 | 2090 660 5500 330 1 1830 1 1 550 | 1 1340 I 670 Grain size% < 1 μιη 60.4 49.4 47.9 45.6 36.0 34.8 1 31.5 38.5 37.6% < 2 μιη 90.6 81.9 79.4 76.2 61.6 1 55.2 | v〇νο 66.7 Os Γ ΟΟ 〇 \ 00 (N as »n ON ^ m 00 VO 00 00 dry matter content (%) 75.5 1 75.9 1 76.0 76.7 75.8 75.1 丨75.i 1 丨 75.2 1 75.5 76.3 1 0.64 1 1.08 1 1.08 1.08 1.08 0.64 f 1.08 ^ 1.08 j 1.08] 1.08 Neutralization conditions 1 70% Na 30% Ca 100% K 70% Na 30% Ca 50% Na 50% Mg 100% AMP 70% Na 30 % Ca Composition without 100% ΤΕΑ 100% NH4 50% K polymer (100% AA 11.8% AA 16% AMA 72.2% MePEG350 100% AA 11.8% AA 16% ΑΜΑ 72.2% MePEG350 test Prior Art of the Invention The Invention of the Invention The Invention of the Invention ^ ρη1λιυ Avoid Mro bismuth and 婶 砩-^-客 沄 £ ¥ Order: Long 0 ^ 〇3% 22 Outfit i: 'Kr ^ VWY Outfit®: Long ¥¥

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200422311 Table VII shows that for the different proportions and nature of the fixed monomer composition and the neutralization system used, the copolymer used in the mineral filler grinding method according to the present invention can significantly improve the optical whitening of coated paper Activation and its whiteness. Moreover, these results also demonstrate that the copolymers according to the present invention can obtain suspensions of mineral fillers which can be treated after storage without agitation. Example 8 This example relates to the use of a copolymer according to the invention in a mineral filler grinding method. It also relates to the use of the resulting suspension in the manufacture of a coating colorant for coating paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, the purpose of this example is to illustrate the different monomer compositions of the copolymers of the present invention. In this example, the first step is to grind a suspension of mineral matter exactly as described in Example 2. Its particle size and its Br00kfieldTM viscosity were determined completely according to the method described in Example 2. The suspension is then added to a composition of a coating colorant, which is obtained by subjecting 100 parts by weight of the dry pigment of the calcium carbonate grinding suspension to dry parts by weight of styrene-butadiene latex ( Sold by DOW Chemical Company under the trade name dl950tm), 0.2 parts of the auxiliary binding agent (sold by CoATEX under the trade name of

Rheocoat (TM) 35) and 1 part by weight of an optical brightener (sold by BAYER Corporation under the trade name Blancophor PTM). Finally, the coating pigment was applied to the paper in accordance with the method described in Example 2, and the coating weight was equal to 15 g / m 2. The paper is a pre-coated paper with a specific gravity of 96 g / m 2 at 21x29.7 cm. 76 200422311 This test illustrates the prior art and implements a homopolymerization of acrylic acid according to the prior art measured with respect to < 65% dry weight relative to mineral filled south 1 = suspension of ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained, in weight percent, particles with straight = less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. This acrylic homopolymer has a specific viscosity of 0.64 and is neutralized by calcium hydroxide and sodium hydroxide.

Test 46 This test illustrates the invention and implements a suspension of a copolymer according to the invention measured to 3: 5% dry weight relative to the dry weight of the mineral filler to ground calcium carbonate. Before milling, the calcium carbonate suspension contained 20% by weight of

The SedigraphTM 5100 grain size analyzer measures particles less than 2 直径 in diameter and has a dry content of 76%. The side copolymer is neutralized with sodium and consists of:

a) 13. 3% acrylic acid and 3.3 ° acrylic acid b) 7 8.4% monomers of formula (I), where: h represents hydrogen for hydrogen R represents methacrylic group R 'for methyl ( 20% dry weight of m + n + p) q = 45 (:) 5% vinyl 0 than pyrrolidone test 47 77 200422311 This test illustrates the present invention and implements the measured relative to the dry weight of the mineral filler. The copolymer according to the present invention is ground to a suspension of about 100% carbonic acid. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 所 as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer is nano-neutralized and consists of: a) 94% acrylic acid and 1% maleic anhydride b) 5% monomers of formula (I), where:

Ri represents hydrogen, R2 represents nitrogen, R represents vinyl, and R 'represents gas (m + n + p) q = l13. Test 48 This test illustrates the present invention and implements a measured 1.50% dry weight relative to the dry weight of the mineral filler. The copolymer according to the invention is a suspension of ground calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 76%. The copolymer is neutralized with sodium and consists of: a) 94% malonic acid and 1% maleic acid b) 2% monomers of formula (I), of which:

Ri stands for hydrogen R2 stands for hydrogen 200422311 R stands for ethylene R 'stands for hydrogen (m + n + p) q = 113 c) 3% of monomers of formula (lib), where R stands for methacrylic group A stands for propylene The radical B represents the methyl group for all tests 45 to 48, the dry matter content t of the mineral substance suspension, its pH value, its particle size identified by weight percentages of particles smaller than} and 2 microns, which at t = 0 and then at t = 8 days Brookfield viscosity (μΐ () and μΐ () ()) were measured under j 〇 and j 〇〇 coffee before and after stirring. According to NF Q 03-038 and NF Q 〇 〇 03 039 standard measurement of quot; r, ^ 457 of the plate, and dagger 57, parameters, and then calculate the difference △ uVcRw + uv / 457 ', and also measured w (CIE according to 1S0 / FDIS 1 1475 standard ) Parameter ° The results that are specific to Type 5 test 45 and test 48 are summarized in Table v 111 79 79 200422311 111¾ Whiteness W (CIE) 90.4 108.2 93.4 92.5 △ UV rn pair · VO »n On R457 + UV 85.2 85.3 85.0 84.9 R457 + UV 89.5 92.4 90.6 90.8 Η Fun ^ ^% ^ §S (¾ 婵 Μίοο 610 720 1790 0 ^ Τ) οο 〇1800 2300 6600 2560 15 ^ ^ ^ ^ Mi! FREE 婵 Μίοο 1580 3730 4120 3880 〇 7100 18000 28000 19000 Brookfield1 M Viscosity (mPa.s) it = 〇4 卩 100 244 570 750 600 Ο I 730 1820 2150 1950 Grain size% < 1 μιη L · 61 ^ 66.9 SS% < 2 μιη 89.3 τ-Η m * σ \ 90.8 93.8 Dry content (%) 78.2 78.3 78.6 75.0 Polymer composition 100% AA 13.3% ΑΑ 3.3% ΑΑ 5% VP 78.4% Μ MePEG2000 94% AA 1% maleic anhydride 5 % Vinyl PEG5000 94% ΑΑ 1% maleic anhydride 2% vinyl PEG5000 3% formula (lib) test prior art / present invention prior art invention present invention number of the invention outfitting ¢: ^ < w I5MO bismuth硪 和 i 镏 装 ® ^ isogCNI ¥ Order: Long < 000g3d3w si§ # ^ o-Outfit: Long < vwv 000

200422311 Table VI11 shows that the copolymers used in the mineral filler grinding method according to the present invention with different monomer compositions can significantly improve the optical whitening activation and whiteness of coated paper. Example 9 This example relates to the use of a copolymer according to the present invention in a mineral filler manufacturing method. It is also about the use of the obtained filler in the manufacture of paper. This embodiment is also related to the measurement of optical whitening and whiteness of the paper thus obtained. Finally, this example is designed to illustrate the effect of the copolymer according to the present invention on improving the activation of optical whitening and the whiteness of the paper produced. In the test corresponding to this example, the first step was to grind a suspension of a mineral substance according to the method described in Example 2. The mineral filler is calcium carbonate. For each test, a fixed amount of abrasive was used, which was either a copolymer according to the present invention or an abrasive of the prior art; this amount was equal to that measured relative to the dry weight of the mineral filler. 35% dry weight copolymer. The particle size of this suspension was measured using a SodigraphTM 5100 particle size analyzer. Its BrookfieldTM viscosity at 10 and 100 rpin was measured according to the procedure described in Example 2 at t = 0 and before and 8 days after stirring. After measuring the viscosity of BrookfieldTM at t = 0, a paper was manufactured with the filler according to the following method. This method produces a pulp of a mixture of 30% by weight of resinous fibers and 70% by weight of california fibers. This paper was refined in a Valley stack at 30 ° SR to a concentration of 16 g / L 81 200422311. The pulp is contained in a Frank-type forming bowl. 1% by weight (relative to the total dry weight of the fiber) of Blancophor P01TM optical brightener sold by BAYER was incorporated into the pulp. Then KeydimeTMC222 gum (sold by EKA Chemical Co., Ltd.) was added at 0.6% by weight relative to the total dry weight of the fiber. A filler in the form of a water-soluble suspension is then added in a proportion of 30% by weight relative to the total weight of the fibers. The resulting material was diluted to obtain a paper having a final gram weight of 80 g / m2. A cationic / polyammonium powder type retention system is also added. The cationic powder is Hi-CatTM 5283 sold by Roquette and Polyacrylamide is PercolTM 178 sold by Ciba. The amount of the retaining agent was adjusted so that the percentage of filler remaining in the obtained paper was 20%. Finally, the r457 + uv and r457_uv parameters 'of the paper produced are determined according to NF Q 03-038 and NF Q 03-039 standards, and then the difference ΔuvsRm + w-R457-UV' is calculated and also determined according to ISO / FDIS 1 1475 w (CIE) Moxibustion number 0 Test 4 9 This test illustrates the previous technique and implements a suspension of 0.33% dry weight of the acrylic homopolymer according to the previous technique to grind calcium carbonate relative to the dry weight of the mineral filler. . Prior to milling, the calcium carbonate suspension contained wt% particles having a diameter of less than 2 μm as measured with a S6dig]: aphTM 5100 grain size analyzer and had a dry matter content of 65%. This acrylic homopolymer has a specific viscosity of 0.64, and is neutralized with about hydroxide and sodium hydroxide. Test 5 0 82 200422311 This test illustrates the invention and implements a suspension according to the invention of 0.35% dry weight of the copolymer according to the invention with respect to the dry weight of the mineral filler. Prior to milling, the carbonic acid # 5 suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 65%. The copolymer has a specific viscosity of 1. 10, is neutralized with sodium and is composed of:

a) 14.1% acrylic acid and 3.4% fluorenyl acrylic acid b) 82 · 5% monomers of formula (I), where: h represents hydrogen R2 represents hydrogen R represents methacrylic acid group R ′ represents methyl Base (m + n + p) q = 45 Experiment 51

This test illustrates the present invention and implements a suspension of a copolymer according to the present invention to grind calcium carbonate at 0.35% dry weight measured relative to the dry weight of the mineral filler. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 65%. The copolymer has a specific viscosity of 1.49, is neutralized with sodium and is composed of: a) 13 · 7 ° /. Acrylic acid and 3.3% fluorenyl acrylic acid b) 83% of monomers of formula (I), where: 83 200422311 h represents hydrogen for hydrogen R for methylpropionate group R 'for methyl (m + n + p ) q = l13 cause test 52 This test illustrates the present invention and implements a suspension of the copolymer according to the invention of 0.35% dry weight measured relative to the dry weight of the mineral filler to grind calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a S6digraphTM 5100 grain size analyzer and had a dry matter content of 65%. The copolymer has a specific viscosity of 1. 2 7 and is neutralized with sodium and is composed of: a) 8.5% propionic acid and 1.5% methylpropionic acid b) 90% of a monomer of formula (I) Body, in which: I represents hydrogen, represents hydrogen, R represents a methacrylic group, and R 'represents methyl (m + n + p) q = l13. Experiment 53 This experiment illustrates the present invention and implements it with respect to the dry weight of mineral fillers. An amount of 0.35% dry weight of the copolymer according to the invention is then ground to a suspension of calcium carbonate. Prior to milling, the calcium carbonate suspension contained 20% by weight of particles having a diameter of less than 2 μm as measured with a SodigraphTM 5100 grain size analyzer and had a dry matter content of 65%. The copolymer has a specific viscosity of 1.56, is neutralized with sodium and is composed of: a) 8.5 ° /. Acrylic acid and 1.5% methacrylic acid b) 90 ° / ◦ monomer of formula (I), where:

Ri represents hydrogen represents hydrogen R represents a methacrylic group R 'represents methyl (m + n + p) q = l13 For all tests 45 to 49, the mineral filler suspension was weighted by particles smaller than 1 and 2 microns The percentage-recognized particle size, its Br00kfieldTM viscosity, measured at t = 0 and then at t = 8 days at 10 and 100 rpm, was determined before and after stirring.

Finally, R457 + uv and R457 of the produced paper were measured according to the NF Q 03-038 and NF 03-039 standards, and the parameter ′ was then used to calculate the difference Δ㈣_. Chuan, and Yimeng so / ms 1 1475 standard determination of w Brightener 1_ △ UV 〇00 \ 0000 00 00 ^ Τ) 00 2 ϊ§ £ g 卩 100 〇rH ο (Ν r * H 490 s 340 荖 w% 2 target 〇 沄 Η 540 3250 480 1620 ϊ§ long g 2 ^ g ^ V 2 PQ 婵 Μίοο Precipitation 220 620 280 430 〇1380 4640 1560 2880 Brookfield ™ viscosity (mPa.s) it = o 卩 100 〇ο 580 230 490 〇450 4440 1160 2500 Grain size% < 1 μιη L29.1 '' 28.3 28.5 29.5 29.3% < 2 μιη L ^ 〇J 58.4 59.0 59.1 59.4 1 0.64] 1.10 1.49 1.27 1.56 Polymer composition! 100% AA 14.1% ΑΑ 3.4% ΑΜΑ 82.5% M MePEG2000 13.7% ΑΑ 3.3% ΑΜΑ 83% Μ MePEG5000 8.5% ΑΑ 1.5% ΑΜΑ 90% Μ MePEG5000 8.5% ΑΑ 丨 1.5% ΑΜΑ 90% Μ MePEG5000 Test previous technology / previous technology of the present invention this invention this invention this invention number σ \ ίη Buried equipment ¢: ^ < w-^ sl— s Buried equipment 肊 砩: 长 & 义 900

200422311 Table XI shows that the copolymer used in the filler manufacturing method according to the present invention can significantly improve the optical whitening activation and whiteness of the manufactured paper. Moreover, these results also demonstrate that the copolymers according to the present invention can obtain suspensions of mineral fillers which can be treated after storage without agitation. Example 10 This example relates to the use of the copolymer according to the present invention as an additive in a method for manufacturing a coating color. It also relates to the use of the coating pigments thus obtained for the manufacture of coated paper. This embodiment is also related to the measurement of optical whitening and whiteness of the coated paper thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymer according to the present invention in improving the optical whitening and whiteness of coated paper. In the test equivalent to this example, the first step was to use a method known to those skilled in the art to mix a suspension of thorium carbonate sold under the trade name SetacarbTM by the company OMYA and HygragrossTM 90 sold by the company Huber. Kaolin mix. Then, 100 parts by weight of dry pigment, 10 parts by weight of styrene-butadiene latex (sold under the trade name of DL950TM by Dow Chemical Co., Ltd.), and 1 part by weight of optics sold by BAYER Co. under the brand name Blancophor PTM The whitening agents are combined to prepare a mixture. Finally, a semi-dry weight of an optical whitening carrier known to those skilled in the art, that is, a polyvinyl alcohol sold by CLARIANT under the trade name of MowiolTM 4-98 is finally added. For each test, the additives according to the invention in the specified proportions may be added or not added. These mixtures were then applied to cold-laminate paper according to the method described in Example 2 with a coating weight equal to 15 g / m2. This paper is 87 200422311 21x29.7 cm \ + colored paper with a specific gravity of 76 g / m². Its white

The characteristics of the degree with parameters! ^, D & ~ 57 + υν, Κ457 ,, Δϋν, and w (CIE) are respectively equal to 90 · 9—83 only 7 1 j 1 W · 8—7.1 and 103.6. Test 5 4 This test describes the previous technique and implements the above-mentioned mixture of mineral filling engraving, the above-mentioned latex and the above-mentioned optical brightener, and the mixture is produced in the ratio defined at the beginning of Example 9. Test 55 This test illustrates the invention and implements the above-mentioned mixture of mineral fillers, the above-mentioned latex, and the above-mentioned optical brightener, and the mixture is produced in the ratio defined at the beginning of Example 9. It also implements 15 dry parts by weight of the copolymer according to the invention in the formulation of the mixture. The copolymer has a specific viscosity of 14.2, is neutralized with sodium and is composed of the following ingredients: a) 13.6% acrylic acid and 3.4% methacrylic acid b) 83% monomer of formula (I), Where: h represents hydrogen, hydrogen represents R, a methacrylic group, R 'represents a fluorenyl group (m + n + p), q = 45, test 56. This test is a mixture that illustrates the present invention and implements the mineral filler 88 200422311 mentioned above. 2. The above-mentioned latex and the above-mentioned optical brightener are used to produce paint colorants in the proportions defined at the beginning of Example 9. It also implements 1 dry weight of the copolymer according to the invention in the formulation of the coating color. The copolymer has a specific viscosity of 4.83, is neutralized with sodium and consists of the following: a) 13.6% acrylic acid and 3.4% methacrylic acid

b) 83% of monomers of formula (I), where:

Ri is hydrogen I is hydrogen R is a methacrylic group R ’is methyl (m + n + p) q = 45 Experiment 57

This test demonstrates the prior art and implements a mixture of the above-mentioned mineral fillers, the above-mentioned latex, and the above-mentioned optical brightener to produce paint pigments in the proportions defined at the beginning of Example 9. It also implements 0.5 dry parts of polyvinyl alcohol as an optical whitening carrier. Test 5 8 This test illustrates the present invention and implements the above-mentioned mixture of mineral fillers, the above-mentioned latex, and the above-mentioned optical brightener to produce coating pigments in the proportions defined in the beginning of Example 9. . It also implements 0.5 dry parts of polyvinyl alcohol as an optical whitening medium in the formulation of § 19 mixtures, as well as the heavy copolymer 89 200422311 of the present invention. The copolymer has a specific viscosity of 14.2, is neutralized with sodium and is composed of: a) 13.6% acrylic acid and 3.4% fluorenyl acrylic acid b) 83% monomer of formula (I), wherein : I represents hydrogen, represents hydrogen, R represents a methyl acrylic acid group, R 'represents a fluorenyl group (m + n + p), q = 45, Test 59. This test is to illustrate the present invention and implement the mixture of mineral fillers mentioned above, The above-mentioned latex and the above-mentioned optical brightener were used to produce coating pigments in the proportions defined at the beginning of Example 9. It also implements 0.5 dry weight of polyvinyl alcohol as an optical whitening medium in the formulation of the mixture, with & " the weight of the copolymer according to the invention. The copolymer has a ratio of 4.83 Viscosity, neutralized with sodium and consisting of: a) 13.6 ° / ❶ acrylic acid and 3.4 ° / ◦methacrylic acid b) 83% monomer of formula (I), where:

Ri represents hydrogen represents hydrogen R represents methyl acrylic acid group 90 200422311 R 'represents methyl (m + n + p) q = 45 For tests 54 to 59, the colorant of the coating pigment obtained at t = 0 Viscosity was measured at 10 and 100 rpm (μ " and Mio). Finally, determine the R457 + uv and R457-UV parameters of the coated cardboard according to NF Q 03-038 and NF Q 03-039 standards, and then calculate the difference AUV = R457 + uv —R457-UV 'and also according to IS0 / FDIS 1 1475 standard determination of w (ciE) parameter 0 The water retention value was determined for each paint pigment according to the method described in EP 1 001 083. The paint pigment was treated in a standardized cylinder at a pressure of 7 bar, and a paper-type surface capable of passing water was installed. Then measure the volume of the mixture filtrate collected after 20 minutes (V2. Cents in milliliters) and the time for the first drop to pass through the filter paper (t-th drop, in minutes) The lower the value of t * -drop, the better the retention. All results corresponding to tests 54 to 59 are summarized in Table X. 200422311 x < Test of the invention On κη goi〇d ο q νο od 66.9 8040 1620 ΓΠ Τ-Η 4'54 1-4 00 〇 \ 84.6 13.5 121.8 Inventive 00 «ο g 〇rH d On d VO od 66.9 6160 1390 5,00 98.2 84.6 13.6 121.7 Previous technology g 〇d Ο ο v 〇od 66.7 1780 430 Γ〇ro 2,01 | L 96.7 1 84.7 12.0 115.1 The present invention in go rH o 〇 qv〇00 66.8 11380 1880 * Bu 2,05 os 1 84.9 10.2 111.2 The present invention ir > i〇goo ο VO od 66.8 8700 1610 丨 ro (N 3,25 1 95.4 1 84.9 10.5 112.2 Previous art ?: gor * H o Ο v od 67.3 2920 550 inch Γ26 1 82.8 00 00 BU 103.3 Compound Setacarb ™ | H | t ffi DL950 ™ Blancophor P ™ PVA 4-98 ™ 13.6% ΑΑ 3.4% ΑΜΑ 83% ΜMePEG20 00 _H4.2) _ 13.6% ΑΑ 3.4% ΑΑΑ 83% Μ MePEG2000 〇1Ga = 4.83) a 0h Dry matter content (%) W OS ο ΧΛ ά \ s 5 1 g P? △ uy | wu Mixture compound filling Emulsion latex optical brightener Optical brightener base Whiteness of coated paper according to the properties of the polymer mixture of the invention s €-

200422311 Table X shows that 'there is nothing to do with the presence or absence of polyethylene enzyme as an optical brightener' The copolymer according to the present invention can significantly improve the optical whitening activation effect of coated paper and improve its whiteness. I have also noticed that the use of the copolymers according to the present invention can significantly improve the water retention of paint pigments. Moreover, we have noticed that the Brookfield viscosity of the coating pigments obtained according to the present invention is compatible with general industrial applications. Example 11 This example relates to the use of the copolymer according to the invention as an additive in the manufacture of suspensions of previously dispersed and / or ground mineral substances. It is also related to the use of the suspension thus obtained in the manufacture of coating pigments, which are used for coating paper. This embodiment is also about measuring the optical whitening and whiteness of the paper thus obtained. Finally, this example is designed to illustrate the effect of the copolymer according to the present invention on improving the optical whitening activation and whiteness of coated paper. In the test corresponding to this example, a calcium carbonate suspension sold under the trade name of HydrocarbTM 90 by the company OMγA was used. The next step is to incorporate in these suspensions the copolymer according to the invention, measured in relation to the dry weight of the mineral filler, into 0% by weight, and then the suspension is added to the coating pigment In the composition. The paint colorant was obtained by selling 100 parts by weight of a dry pigment, 10 parts by weight of a styrene-butadiene latex (sold by Dow Chemical Company, trade name DL920TM), and 1 part by weight of BAYER. Trade name 93 200422311

Blancophor PTM optical brighteners are combined. This coating color was then applied to the paper in accordance with the method described in Example 2 so that the coating weight was equal to 15 g / m2. The paper was a pre-coated paper with a specific gravity of 21 x 29 · 7 cm and 96 g / m 2. The characteristics of its whiteness are expressed by parameters R457 + uv, R457 ,, Δυν, and W (CIE), which are respectively equal to 88 · 4—85. 8—2 · 6 and 89.5. Its viscosity is measured by the same method as that applied to an aqueous suspension of a mineral substance. The paper was coated exactly as described in Example 2. Test 60 This test demonstrates the prior art and implements Hydrocarb90TM calcium carbonate suspension in the manufacture of paint pigments. Test 61 This test illustrates the present invention and implements a copolymer according to the present invention measured as u dry weight relative to the dry weight of the mineral filler as an additive in a Hydrocarb 90 TM calcium carbonate suspension. The copolymer has a specific viscosity of 1.52, is neutralized with sodium and is composed of: a) 8.5% acrylic acid and ΐ · 5% methacrylic acid b) 90% of the monomer of formula (I), of which: H for hydrogen h for hydrogen R for fluorenylpropanoic acid group R 'for fluorenyl 94 200422311 (m + n + p) q = 113 Test 62 This test illustrates the prior art and implements Hydro in the manufacture of paint pigments O Carb90TM calcium carbonate suspension. It also implements 1 dry part (for 100 parts by weight of dry pigment) of a prior art optical whitening vehicle in the manufacture of coating pigments, that is, polyvinylpyrrolidone sold under the trade name of K30tm by BASF. Test 63

This test illustrates the invention and implements the copolymer according to the invention as an additive in a Hydrocarb90TM carbonic acid # 5 suspension, measured at 1% dry weight relative to the dry weight of the mineral filler. The copolymer has a specific viscosity of 1.5 2 and is neutralized in nanometers and is composed of: a) 8.5% acrylic acid and 1.5% methacrylic acid b) 90% monomer of formula (I), wherein:

D represents hydrogen, h represents hydrogen, R represents a methacrylic group, and R 'represents methyl (m + n + p) q = 113. It is also applied in the manufacture of paint pigments in a dry weight of 1 part (for 100 parts by weight). Dry pigment) is a prior art optical whitening vehicle, which is a polyvinylpyrrolidone sold by BASF under the trade name K30TM. Reverse test 64 95 200422311 This test illustrates the previous technique and implements Hydrocarb 9 (P calcium carbonate suspension in the manufacture of paint pigments. It also implements 1 dry weight (for 100 parts by weight of dry pigment in the manufacture of paint pigments). ) Of the prior art optical brightening vehicle, that is, methoxy polyethylene glycol with a molecular weight of 5000. Test 6 5 This test illustrates the invention and implements the basis for measuring the 1% dry weight relative to the dry weight of the mineral filler. The copolymer of the present invention is used as an additive in Hydrocarb 90TM calcium carbonate suspension. The copolymer has a specific viscosity of 1.52, is neutralized with sodium and is composed of the following: a) 8.5% acrylic acid and 1.5% Methacrylic acid b) 90% monomer of formula (I), where: d represents hydrogen R2 represents hydrogen R represents methacrylic group R 'represents methyl (m + n + p) q = 113 which is also used in paint color In the manufacture of raw materials, the prior art optical brightening vehicle of dry weight (for 100 parts by weight of dry pigment) is used, that is, ethoxylated polyethylene glycol with a molecular weight of 5000. For all tests 60 to 65, the viscosity of the mixture obtained at t = 0 was determined at 10 and 100 rpm (μΗ and Η. Finally, the I? Of the paper produced was determined according to NF Q 03-038 and NF Q 03-039 standards. 457 + υν and R457_uv parameters, and then calculate the difference △ 丨 丨 v —κ457 + υν-96 200422311 4 5 7_uv, and also determine the W (CIE) parameter according to ISO / FDIS 1 1475. All pairs are equal to the results of tests 60 to 65 They are all extracted in Table XI.

97 200422311 3 Test the invention 〇T-4 〇1-Η τ-Η rH ο Os 00 67.0 1750 360 96.3 85.5 10.7 114.2 The invention 〇1-H 〇ψ ^ 4 1-Η Ο r «H σ \ ο VO od 66.9 650 310 Γ 95.3 85.5 1 00 Os 110.0 Previous art 2 〇 ▼ -Η 'ο ο Bud 67.0 2650 550 98.3 85.5 12.7 119.8 The present invention S 〇tH Ο 1—Η ^ Η ο ο VO od 67.1 750 200 1_ 96.6 85.2 11.4 114.7 The present invention S Ο Ο ο τ-Η Bud 67.0 650 230 1___? 5J! 85.6 〇 \ Ον 110.7 Prior art S Ο Ο τ-Η Ο 00 67.1 640 τ-Η 1 90.8 1 85.3 92.6 Hydragross ™ 90 DL920 ™ Blancophor ™ 8.5% ΑΑ 5% ΑΜΑ 90% Μ MePEG5000 Κ30 ™ Μ MePEG5000 ffi Pm Dry content (%) CO Λ Ο CO cd 8 τ δ & AUV U Filler suspension latex optical brightener according to Whiteness of coated paper with other additives of the present invention 1 Properties of coating mixture 1 Blend ve: ^ < w. · ^^ ooos «s 006

200422311 Table XI shows the optical whitening activation and soya whiteness of the modified end product by adding the copolymer according to the present invention in a mineral substance suspension as an additive. Moreover, I have also noticed that the Brookfield viscosity of the coating pigments obtained according to the present invention is compatible with general industrial applications. Example 12 This example relates to the use of the copolymer according to the present invention as an additive in a manufacturing method of a coating color, and more specifically as an auxiliary binder. This embodiment also relates to the measurement of optical whitening and whiteness of the coated paper thus obtained. Finally, this example is designed to illustrate the effectiveness of the copolymer according to the present invention in improving the optical whitening and whiteness of coated paper. In the test corresponding to this example, a calcium carbonate suspension sold under the trade name HydroCarbTM 90 sold by the company OMYA was added to the composition of the coating color.泫 The paint colorant is made by adding 100 parts by weight of dry pigment, 10 dry wounds of styrene-butadiene latex (sold by Dow Chemical Company, trade name: DL950TM), and auxiliary combination to be tested. Agent dosage and! A part by weight of an optical brightener sold by Bayer under the trade name Blancophor PTM was combined and prepared. 0 The paper was coated with the coating colorant according to the method described in Example 2, and the coating weight was 15 g / m 2. The paper was a pre-coated paper having a specific gravity of 96 g / m 2 at 21 × 29.7 cm. Its viscosity is measured according to the same method as that applied to a water-soluble suspension of a mineral substance. 99 200422311 The paper was coated exactly as described in Example 2. Test 6 6 This test is an explanation of the prior art and was implemented in the manufacture of coating pigments. 0.2 parts of the auxiliary bonding agent of the prior art (sold by the company CoATEX under the trade name RheocoatTM 35). Test 67 This 4 test system illustrates the present invention and is implemented in the manufacture of coating pigments. • 2 parts of the copolymer according to the present invention as an additive auxiliary binder.

The copolymer is neutralized with sodium and consists of: a) 5.9% propionic acid and ι · 6% fluorenyl acrylic acid b) 92.5% monomers of formula (I), of which:

Ri represents hydrogen, h represents hydrogen, R represents a methacrylic group, and represents methyl (m + n + p) q = 113

This test is to illustrate the present invention and implement it in the manufacture of paint pigments. The copolymer according to the present invention, which is the same as that performed in Test 67, is used as an auxiliary auxiliary binder.

J-type test fi Q This test is to illustrate the present invention and implement 3 parts of the copolymer according to the present invention as an additive auxiliary binder in the manufacture of coating pigments as in Test 67. 100 200422311 Test 70 This test is to illustrate the present invention and to implement 4 parts of the same as those implemented in Test 67 in the manufacture of coating pigments. The copolymer according to the present invention is used as an auxiliary auxiliary binder. 9 The test point is at 10 And 100 rpm (μΗ and μ⑽⑽). Finally, according to NF Q 03-038 and NF Q 03-039 standards, set the K57 + υν and R457_uv parameters of the cardboard, and then calculate the difference.

~ R457, uv, and also according to ISO / FDIS 1147R. Cake standard determination W (CIE) 4 corresponds to the test 66 π spoon and is recorded in Table XII

101 200422311

Table XII Prior Art The present invention The present invention The compound of the paint pigment of the present invention Compound 66 66 68 69 70 Filler Hydrogloss ™ 90 100 100 100 100 100 Latex DL950 ™ 10 10 10 10 10 Optical Brightener Blancophor P ™ 1 1 1 1 1 Auxiliary binder Rheocoat ™ 35 0.2 0 0 0 0 Polymer according to the invention 0 0.2 0.8 3.0 4.0 Properties of the mixture pH 8.5 8.5 8.5 8.6 8.6 Content (%) 66.8 67.0 67.0 67.0 65.0 p10mPa.s 25200 8030 16000 34600 43200 p100mPa.s 3700 1470 2510 6430 6300 White coated paper R457 + UV 89.7 91.3 91.5 92.2 92.5 degrees R457 -IJV 85.5 85.3 85.2 85.1 85.3 △ uv 4.2 6.0 6.3 7.1 7.2 W (CIE) 88.6 94.2 97.2 101.3 101.1 Table X11 shows that the copolymer according to the present invention can significantly improve optical whitening activation and whiteness of coated paper as an additive in a coating colorant. 102

Claims (1)

200422311 Scope of application for patent: Seed water 'the use of cereal copolymer as a reagent for improving optical whitening'. The special feature is that the copolymer has at least one alkoxy group or hydroxypolyalkylene monohydric alcohol which can be grafted. On at least one ethylenically unsaturated monomer. 2. The use of a water-soluble copolymer according to the scope of the patent application as an agent for improving optical whitening, characterized in that the copolymer is composed of at least one monomer of formula (I): (I) where m — P represents the number of alkylene oxide units, which is less than or equal to 150, η represents the number of ethylene oxide units, which is less than or equal to ι50, q represents specialization at least 1 and makes 5 < (m + n + p) q < l 50, and preferably an integer such that 15 $ (m + n + p) qsi20, one Ri represents hydrogen or fluorenyl or ethyl, and h represents hydrogen or fluorenyl or ethyl,- R represents a group containing a polymerizable unsaturated function, and belongs to the group of vinyl and acrylic, fluorenyl acrylic, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl phthalate, and Ethyl urethane unsaturated compounds such as ethyl urethane, methacrylic urethane, α-α'diamidyl-isopropenyl-benzylamino urethane and allyl Groups of ethylaminoacetate, and substituted or unsubstituted allyl or ethylene groups 103 200422311 groups, or groups of dilute unsaturated ethylamines or amines,- Represents hydrogen or a hydrocarbon group having i to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably has! Nicotyl to 4 carbon atoms. 3. Use of a water-soluble copolymer as an optical whitening agent according to any one of item 1 or 2 of the scope of the patent application, characterized in that the copolymer is composed of the following: a) at least one Anionic monomers having carboxylic or dicarboxylic acid or phosphoric acid or phosphonic acid or sulfonic acid functions or mixtures thereof, b) at least one non-ionic monomer, the non-ionic mono system consisting of at least one monomer of formula (I) : (I) where t —m and P represent the number of alkylene oxide units, which is less than or equal to 1 50, —η represents the number of ethylene oxide units, which is less than or equal to 15 0, and —Q represents at least 1 and makes 5 ^ ( m + n + p) q < 150, and preferably 疋 such that 15S (m + n + p) d20 is an integer, Ri represents hydrogen or methyl or ethyl, and h represents hydrogen or methyl or ethyl,- R represents a group containing a polymerizable unsaturated functional group, which belongs to the vinyl group and acrylic acid, fluorenyl acrylic acid, maleic acid, and decomposition of urethane 104 200422311 cephalic acid, crotonic acid, and ethyl acetate Groups, and ethyl urethane unsaturated compounds such as acryl urethane, methacryl urethane, α-α 'dimethyl-isopropenyl urethane, and Groups of allylaminomethyl ethyls, as well as groups of substituted or unsubstituted dilute propyl or ethylene scales, or groups of ethylenically unsaturated amides or fluorimines Group, one R ′ represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents i to A hydrocarbon group of 4 carbon atoms, or a mixture of several monomers of formula (I), c) if possible, at least one monomer or derivative thereof in the form of acrylamide or methacrylamide, such as N- [3 — (Dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamine and mixtures thereof, or at least one water-insoluble monomer, such as alkyl acrylate Esters or alkyl methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate or two dilute fee N- [2- (dimethylamino) ethyl ] Esters, ethyls such as ethyl acetate, vinylpyrrolidone, styrene, α-methylstyrene and derivatives thereof, or at least one cationic monomer or quaternary ammonium, such as gasification or sulfuric acid [ 2- (Methenoyloxy) ethyl] trimethylammonium, gasified or sulfuric acid [2- (propylene fluorenyloxy) ethyl] trimethylammonium, gasified or sulfuric acid [3- (propylenefluorene) Amino) propyl] trimethylammonium, chlorinated or dimethyldiallylammonium sulfate, gasified or sulfuric acid [3-mono (methacrylamino) propyl] trimethylammonium, or at least one Organic fluorinated or organosilicated monomer Or a mixture of several of these monomers, d) if possible, at least one monomer having at least two ethylenically unsaturated compounds, referred to as a crosslinking monomer, 200422311 ingredients a), b), c) and d The sum of the ratios is equal to 1000 / 〇. 4. The use of the copolymer according to item 3 of the patent application as a reagent for improving optical whitening, characterized in that the organosiliconized single system is selected from a molecule of formula (Ila) or (lib). Molecule of formula (Ila) is% nr- 0 ίΐ κ ″. A--Si — Ο- Si— I R9 Where -ml, pi, m2, and P2 represent the number of alkylene oxide units, which are less than or equal to 150,-nl and π2 represent the number of ethylene oxide units, which are less than or equal to 150, and ql and Q2 represent at least equal to 1 and such that 0 < (ml + nl + pl) qK150 and 〇 $ (m2 + n2 + p2) q2sl50, -r represents a number that makes Krs2〇, -h represents a group containing a polymerizable unsaturated function, belongs to Vinyl groups and groups of acrylic acid, methacrylic acid, cis-butenedioic acid, decomposed aconitic acid, crotonic acid, and vinyl peptidic acid esters, and ethyl acetic acid unsaturated compounds such as acrylamino fluorene Acid ethyl ester, fluorenyl acryl urethane, α-α 'difluorenyl-isopropenyl-benzyl amine urethane and allyl urethane ethyl ester group' and substituted or Unsubstituted propyl or vinyl scale groups, or groups of ethylenically unsaturated fluorene or imimine, where h, R5, R! 0 and Ru represent hydrogen or methyl or ethyl The group 106 200422311 'Re, R7, Rs, and R9 represents a straight-chain or branched alkyl, aryl, or aryl group having 1 to 20 carbon atoms or Alkyl, or a mixture thereof, R12 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms,-A and B are groups that may be present, in this case, they represent a hydrocarbon group having 1 to 4 carbon atoms, (Lib) is R-A-Si (〇B) 3 where one R represents a group containing a polymerizable unsaturated function, which belongs to the vinyl group and acrylic acid, methacrylic acid, cis-butenedioic acid, and decomposed aconite Groups of I, crotonic acid, and vinyl phosphonates, and urethane unsaturated compounds such as acryl urethane, methacryl urethane, α-α 'dimethyl-iso Groups of propenyl-benzyl urethane and allyl urethane, and substituted or unsubstituted allyl or vinyl groups' or ethylenically unsaturated hydrazones A group of amines or imines,-A is a possible group, in which case it represents a hydrocarbon group having 1 to 4 carbon atoms,-B represents a hydrocarbon group having 1 to 4 carbon atoms, or A mixture of several of these monomers, and the crosslinked monomer system is selected from ethylene dimethacrylate, tricyclic Propane triacrylate, allyl acrylate, allyl-maleic acid, methylene-bis-acrylamide, methylene-bis-methacrylamine, tetraallyloxyethyl Group consisting of alkane, triallyl cyanurate, allyl ethers made from polyhydric alcohols such as neopentyl tetraol, sorbitol, sucrose, or a molecule selected from the formula (111) : (III) where p3 and p4 represent the number of alkylene oxide units, 1 is less than or equal to 150,,, n3, and π4 represent the number of ethylene oxide units, which are less than or equal to ⑽, and q3 and q4 represent at least equal to i and such that 0_ 3 + n3 + p3) Q3u50 and an integer of k (m4 + n4 + p4) q "i50. One r 'represents a number such that 1? 4200, and -R! 3 represents a polymerizable unsaturated Group, which belongs to the group of ethylene f and propylene, methacrylic acid, maleic acid, decomposed member 8 croton®, and vinyl acetate, and urethane is not Saturates such as the group of allyl urethane, methacryl urethane, oc-oc monomethyl-isopropenyl-benzyl urethane and allyl urethane, And groups of substituted or unsubstituted allyl or vinyl bonds' or groups of ethylenically unsaturated fluorenes or fluorimines,-Ru, R15, R20 and R21 represent hydrogen or methyl R16, R17, R18, and R19 represent a straight or branched alkyl, aryl, alkaryl, or aralkyl group having 1 to 20 carbon atoms Or a mixture thereof,-D and e are possible groups, in this case, they represent a hydrocarbon group having 1 to 4 carbon atoms, 108 200422311 or a mixture of several such monomers, 5. The use of the water-soluble copolymer according to item 丨 or item 2 as a reagent for improving optical whitening, which is characterized in that the copolymer is composed of the following and is expressed by weight: a) 2% to 95% and more particularly 5% to 90% of at least one ethylenically unsaturated anionic monomer having a monoacid function, which is selected from the group having a monoacid function such as acrylic acid or methacrylic acid or Dibasic acid half esters such as cis-succinic acid or C! To (: 4 monoester ethylenically unsaturated monomers, or mixtures thereof, or selected from dicarboxylic acid functions such as crotonic acid, Isocrotonic acid, cinnamic acid, decomposed aconitic acid, maleic acid or carboxylic acid anhydrides such as ethylenically unsaturated monomers of cis-succinic anhydride, or selected from sulfonic acid functions such as propylamine -Methyl-propane-Luteolinic acid, ethyl methyl dipropionate, ethylenic acid and styrene sulfonic acid, ethylenically unsaturated monomers, or selected from phosphoric acid functions such as vinyl acid, methyl Ethylene phosphate monoacrylate, methacrylate propylene phosphate, acrylate acrylic acid phosphate, acrylate acrylic acid phosphate and ethoxylates of ethylenically unsaturated monomers, or selected from phosphonic acid functions such as ethylene Ethylenically unsaturated monomers of phosphonoic acid, or mixtures thereof, b) 2% to 95 ° /. And more particularly at least one non-ionic ethylenically unsaturated monomer of formula (I) of 5% to 90%: wherein R 0〆 (I) R, 109 ^ P represents the number of alkylene oxide units, which is less than or equal to 150, represents the number of ethylene oxide units, which is less than or equal to 150, Θ < the table is equal to at least 1 and makes 5S (m + n + p) q < 150, and preferably 疋 is called m + n + p) q— < 12. An integer, where Ri represents hydrogen or methyl or ethyl, —I represents hydrogen or methyl or ethyl, and R represents a group containing a polymerizable unsaturated functional group, which belongs to the vinyl group and acrylic, methyl acrylic Acid, maleic acid, decomposed croton crocodile, and vinyl phosphonate groups, as well as ethyl urethane | Unsaturates such as acryl urethane, acryl urethane The group of ethyl ester α α monomethyl-isopropenyl-benzyl urethane and allyl urethane, and the group of substituted or unsubstituted allyl or vinyl earth ' Or a group of unsaturated bonds of amidines or amines,-R 'represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and More preferably, it represents a hydrocarbon group having 1 to 4 carbon atoms, m or a mixture of several monomers of formula (I), c) 0% to 5% of at least one monomer in the form of acrylamide or methacrylamide Or its bamboo organisms' such as N- [3- (diamidoamino) propyl] propanamine or N- [3- (diamidoamino) propyl] methylpropane Melamine and mixtures thereof, or at least one water-insoluble monomer such as alkyl acrylate or methacrylate, unsaturated esters such as N- [2- (diamidoamino) ethyl methacrylate] Ester or N- [2- (diamidoamino) ethyl] acrylate, ethylene such as vinyl acetate, vinylpyrrolidone, styrene, α-methylstyrene and its derivatives, or at least one kind of cation of 110 200422311 Monomer or quaternary ammonium, such as gasified or sulfated [2- (methacryloxy) ethyl] trimethylammonium, gasified or sulfated [2- (propylenepropyleneoxy) ethyl] trimethyl Ammonium, chlorinated or sulfate [3- (propenylamino) propyl] trimethylammonium, vaporized or monomethylallyl sulfate, vaporized or sulfuric acid [3-mono (methacrylamino) ) Propyl] triammonium ammonium, or at least one organic fluorinated or organic silylated monomer, which is preferably selected from molecules of the formula (Ila) or (lib). The molecule of the formula (I la) is -ml, pi, m2, and p2 represent the number of alkylene oxide units, which are less than or equal to 150,-nl and n2 represent the number of ethylene oxide units, which are less than or equal to ι50, and Q1 and q2 represent at least equal to 1 and make OS (ml + nl + pl) (ji magic 50 and 〇ym2 + n2 + p2) q2 <15; an integer, one r represents a number such that lSrS200, and one h represents a group containing a polymerizable unsaturated function, Belongs to the group of ethyl acetate and acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, bataconic acid, and vinyl peptidic acid esters, as well as ethyl acetate unsaturated compounds such as propylene Groups of urethane, methacrylic urethane, methyl-isopropenyl-benzyl urethane, and allyl urethane, and substituted or unsubstituted Allyl or vinyl arsenite-,,,, and 'or a group of ethylenically unsaturated amines or amimines, 111 200422311, r5, R10 and ru represent hydrogen or methyl or ethyl, Re, R7, R8, and R9 represent a straight or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an alkaryl group, or Alkyl, or a mixture thereof,-Ri2 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and A and B are possible groups, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms Where the formula (I lb) is R-A-Si (〇B) 3 where one R represents a group containing a polymerizable unsaturated function, which belongs to the vinyl group and propionic acid, methacrylic acid, cis-butene Groups of diacids, decomposed aconitic acid, crotonic acid, and vinyl acid esters, and ethyl amino unsaturated esters such as ethyl acrylamidoate, ethyl methacrylamidoate, α- a group of α'dimethyl-isopropenyl-benzyl urethane and allyl urethane, and a group of substituted or unsubstituted allyl or vinyl ether, or Group of ethylenically unsaturated amidines or amidoimines, -A is a group that may be present, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms, and -B represents a group having 1 to 4 A hydrocarbon group of one carbon atom, or a mixture of several of these monomers, d) at least one crosslinking monomer from 0% to 3%, which is selected from dimethyl Ethylene acrylate, trihydroxypropane triacrylate, allyl acrylate, allyl maleate, methylene-bis-acrylamide, methylene-bis-methacrylamine, tetramethylene A group consisting of allyloxyethane, tri-n-propyl cyanurate, polyalcohol, 200422311 alcohols such as neopentyl tetraol, shanius k — ^ ^ glycosides, sugars or other allyls Group or selected from formula ⑴. Molecules: Basis Rl3, (III) "Q4 where m3, P3, M, and P4 represent the number of alkylene oxide units, which are less than or equal to 150, and--n3 and n4 represent the number of ethylene oxide units, which are less than or equal to 150, and y and q4 represent at least equal to 丨And make 0S (m3 + n3 + p3) q3sl50 and 0s (m4 + n4 + p4) q4sl50 an integer, -r 'represents a number such that Br, s2OO, -Ru represents a polymerizable unsaturated function Groups belonging to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconite, crotonic acid, and vinyl esters, and ethyl urethane unsaturated compounds Such as the groups of acryl urethane, methacryl urethane, α-α 'dimethyl-isopropenyl-benzyl urethane and allyl urethane, and Groups of substituted or unsubstituted allyl or vinyl ethers, or groups of ethylenically unsaturated fluorenes or fluorimines,-Rl4, Rl5, R20 and represent hydrogen or methyl or ethyl -R16, R17, R18, and R! 9 represent a straight-chain or branched alkyl, aryl, or alkylaryl group having 1 to · 20 carbon atoms Or aralkyl, or a mixture thereof,-D and E are possible groups, in which case they represent a hydrocarbon group having 113 200422311 having 1 to 4 carbon atoms, or a mixture of several such monomers, the ingredients The sum of the proportions of a), b), c) and d) is equal to 100%. 6. The use of a water-soluble copolymer according to any one of the scope of the patent application item 丨 or 2 as an agent for improving optical whitening, characterized in that the copolymer is in its acid form or has one or more monovalent compounds The neutralizing agent is completely or partially neutralized with a functional or polyvalent neutralizing agent, for example, for monovalent functionalities, the neutralizing agent is selected from basic cations, especially sodium, potassium, lithium, " ammonium Or primary, secondary or tertiary aliphatic and / or cyclic amines, such as stearylamine, ethanolamines (mono, di-, triethanolamine), mono and diethylamine, cyclohexyl, methyl% Hexylamine, aminomethylpropanol, or a group consisting of, or, 'for polyvalent functions, the neutralizing agent is selected from the group consisting of soil divalent cations', especially magnesium and calcium, or zinc and Trivalent cations include groups consisting especially of certain higher valent cations. — 7 · A reagent for improving optical whitening, which is characterized in that it is a water-soluble copolymer in which at least one di-unsaturated monomer is substituted with at least one oxy-fluorenyl-polyalkylene group. According to the scope of the patent application (7), the improved optical gain is characterized in that it is a water-soluble co-polymer composed of at least ―type ⑴ monomers. , α (I) R, 114 200422311 m σ P represents the number of alkylene oxide units, which is less than or equal to 15 0, n represents the number of ethylene oxide units, which is less than or equal to 1 50, and Q represents at least 1 and makes 5 ^ (m + n + p) q ^ 150, and preferably an integer of 15s (m + n + p) qs12〇, one Ri represents hydrogen or methyl or ethyl, h represents hydrogen or methyl or ethyl — —R represents a group containing a polymerizable unsaturated functional group, which belongs to the group of vinyl group and acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl peptidate And ethyl urethane unsaturated compounds such as acryl urethane, methacryl urethane, α-α'dimethyl-isopropenyl-benzyl urethane and allyl Groups of ethylaminoacetate, and groups of substituted or unsubstituted allyl or vinyl groups 'or groups of ethylenically unsaturated fluorenamines or fluorimines, where R' stands for Hydrogen or a hydrocarbon group having 1 to 40 carbon atoms. 9. The reagent for improving optical whitening according to any one of item 7 or 8 of the scope of patent application, characterized in that it is a water-soluble copolymer consisting of: a) at least one having a carboxylic acid or a dicarboxylic acid or Phosphoric acid or phosphonic acid or sulfonic acid-functional anionic monomer or a mixture thereof, b) at least one non-ionic monomer, the non-ionic monosystem consists of at least one monomer of formula (I): 200422311 R (I) where m and P represent the number of alkylene oxide units, which is less than or equal to 15 and n represents the number of ethylene oxide units, which are less than or equal to 150, Q represents an integer equal to at least 1 such that 5 < (m + n + p) q ^ l50, and preferably an integer such that 15s (m + n + p) (^ 12), Ri represents hydrogen or fluorenyl or ethyl -R2 represents hydrogen or fluorenyl or ethyl, -R represents a group containing a polymerizable unsaturated function, and belongs to the group of vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and vinyl acid esters, And ethyl urethane unsaturated compounds such as ethyl acrylamidoacetate, ethyl methacrylamidoacetate, α-αdimethyl-isopropenyl-benzylaminoacetate, and ethylpropyl Groups of urethanes, and groups of substituted or unsubstituted allyl or vinyl groups, or groups of ethylenically unsaturated amines or amines, -R ' Represents a hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrocarbon group having 1 to 4 carbon atoms, or several formulae (I ) A mixture of monomers, c) if possible, at least one monomer in the form of acrylamide or methacrylamine 116 200422311 or a derivative thereof, such as N- [3- (dimethylamino) propyl] propylene Amidine or N- [3- (dimethylamino) propyl] methacrylamidine and mixtures thereof, or at least one water-insoluble monoamine , Such as alkyl acrylate or alkyl methacrylate, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate or N- [2- (dimethylamino) acrylate Ethyl] esters, vinyls such as vinyl acetate, vinyl [1-pyrrolidone, styrene, α-fluorenylstyrene and derivatives thereof, or at least one cationic monomer or quaternary ammonium, such as gasification Or [2- (methacryloxy) ethyl] trimethylammonium sulfate, chlorinated or sulfuric acid [2- (propyleneacryloxy) ethyl] trimethylammonium, chlorinated or sulfuric acid [3-( Acrylamido) propyl] trimethylammonium, vaporized or dimethyldiallylammonium sulfate, chlorinated or sulfuric acid [3-mono (methacrylamido) propyl] trimethylammonium, Or at least one organic fluorinated or organosilicated monomer, or a mixture of several of these monomers, d) if possible, at least one monomer having at least two ethylenically unsaturated compounds, referred to as a crosslinked monomer The sum of the proportions of components a), b), c) and _d) is equal to 100%. 1 0. An improved optical whitening agent according to item 9 of the Shenjing patent, characterized in that the organosilicidation single system is selected from the molecules of formula (IIa) or (nb): The molecule of formula (Ila) is rR9 must be "乜" P! where -ml, p, m2 and P2 represent the number of alkylene oxide units, which are less than or equal to 117 200422311 at 150,-nl and n2 represent the number of ethylene oxide units, which are less than or equal to ι50. -ql and q2 represent integers that are at least equal to 1 such that OS (ml + nl + pl) ql ^ 50 and 0s (m2 + n2 + p2) q2sl50, -r represents a number such that 1, and I represents an aggregate Unsaturated functional groups belonging to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconite & L, ugly acid, and vinyl phosphonate, and amino formic acid Ethylethylunsaturates such as Ethylpropylammoniumacetate, Ethylmethylmethacrylate, § α α-Ethyl-isopropenyl-benzylaminocarbamate and allylamino V "Groups" and substituted or unsubstituted allyl or vinyl groups "or groups of ethylenically unsaturated fluorenes or fluorimines, R4, R5, R10 and R " Represents hydrogen or methyl or ethyl, and R, I? 6, 7, Rs, and h represent a straight-chain or knife-branched alkyl group having 1 to 20 carbon atoms. Aryl, alkaryl or aralkyl, or mixtures thereof, R12 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and groups A and B may exist, in this case, their A hydrocarbon group of 1 to 4 carbon atoms, the formula (lib) is R-A-Si (OB ', where gan and R represent a group containing a polymerizable unsaturated function, which belongs to the ethidium group and two groups. Knowledge of the text, methacrylic acid, cis-butenedioic acid, decomposition of aconite, crotonic acid, poly •, and vinyl peptidate, and aminoaminoethyl esters 118 200422311 Groups of substances such as ethyl acryl urethane, ethyl methacryl urethane, α-α 'dimethyl-isopropenyl-vatyl urethane and allyl urethane Groups, as well as groups of substituted or unsubstituted allyl or vinyl ethers, or groups of ethylenically unsaturated fluorenes or fluorimines, where A is a possible group, and here In the case, it represents a hydrocarbon group having 1 to 4 carbon atoms, -B represents a hydrocarbon group having 1 to 4 carbon atoms, or several kinds of the monomer Mixture, and the crosslinked monosystem is selected from ethylene dimethacrylate, trihydroxypropane triacrylate, allyl acrylate, allyl cis-butadiene, methylene-bis-propylene Amine, methylene-bis-methacrylamide, tetraallyloxyethane, triallyl cyanurate, alkenes prepared from polyhydric alcohols such as neopentyl tetraol, sucrose, and sucrose A group of propyl ethers or a molecule selected from formula (III) ... (III) where m3, p3, m4, and p4 represent the number of alkylene oxide units, which are less than or equal to 150, and net n4 represents the number of ethylene oxide units, which is less than or equal to, q q4 represents at least equal to 1 and makes ^ 3 + n3 + P3) q3 phantom 50 and an integer of 0 ^ 4 + η4 + ρ4) _ΐ50, 119 200422311 —Γ 'represents a number that makes Kr, S200, and Ru represents a group containing a polymerizable unsaturated function, which is a vinyl group Groups and groups of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, pentaconic acid, and vinyl phthalates, and ethyl urethane unsaturated compounds such as ethyl propyl methionate Group of esters, methacryl urethane α α monomethyl-isopropenyl-benzyl urethane, and allyl urethane ethyl acetate 'and substituted or unsubstituted allyl Groups of vinyl or vinyl ethers, or groups of ethylenically unsaturated amines or amines,-Rh, R15, ho and R21 represent hydrogen or methyl or ethyl, -R16 'R17, and R19 represents a straight-chain or branched halo, aryl, halo or aryl group having 1 to 20 carbon atoms, or The mixture j - D and E are groups which may be present, in this case, which represents having from 1 to 4 carbon atoms, or a mixture of several kinds of the monomer. 11 · An improved optical whitening agent according to item 7 or 8 of the scope of the patent application, characterized in that the water-soluble copolymer is composed of the following, expressed by weight · a) 2% to 95% and More particularly from 5% to 90% of at least one ethylenically unsaturated anionic monomer having a monocarboxylic acid function, which is selected from monocarboxylic acid functions such as acrylic acid or methacrylic acid or a dibasic acid half ester such as cis —Butenedi = or ethylenically unsaturated monomer from Cl to q monoacetate that decomposes aconitic acid, a mixture of two, or selected from dicarboxylic acid functions such as crotonic acid, " Decompose aconitic acid, maleic acid or carboxylic acid anhydrides such as cis-butenedi 120 200422311 anhydrides of ethylenically unsaturated monomers, seven, strong body, or selected from sulfonic acid functions such as acrylamide Ethyl-unsaturated dendrites of methyl-methyl-propane-lysine, methamphetamine, sodium succinyl allyl sulfonate, ethylene sulfonic acid and styrene sulfonic acid., A. ^ I and early Body, or selected from phosphoric acid functions such as vinyl phosphoric acid, phosphoric acid methacrylate, W ^^^^, methylpropyl Phosphonic acid, acrylic acid, acrylic acid, ethylene glycol, acrylic acid, acrylic acid, propylene phosphate, and ethylenically unsaturated monomers of its ethoxylates, 洸 + 'or remotely have phosphine Acid-bonded unsaturated bond monomers such as vinylphosphonic acid, or mixtures thereof, b) 2% to 95% and more particularly 5% to 90% of at least one non-ionic ethylenically unsaturated monomer of formula ⑴: R, 〇, (I) where m and p represent the number of alkylene oxide units, which is less than or equal to 15 〇, η represents the number of ethylene oxide units, which is less than or equal to 丨 50, Q represents equal to at least 1 and makes 5 < (m + n + p) q ^ l 50, and preferably an integer such that 15s (m + n + p) q $ 12. One Ri represents hydrogen or methyl or ethyl, and h represents hydrogen or methyl or Ethyl, R represents a group containing a polymerizable unsaturated functional group, which belongs to the vinyl group and two dilute acids, methyl acrylic acid, maleic acid, decomposed croton crocetin, and ethanoic acid Groups of esters, and ethyl carbamate 121 200422311 Ester unsaturated compounds such as allyl urethane, methacryl urethane, α-α 'dimethyl-isopropenyl-benzyl amine Groups of ethyl esters and allyl urethanes, as well as groups of substituted or unsubstituted allyl or vinyl ethers, or ethylenically unsaturated fluorene or imimine Group,-R 'represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents 1 to 4 carbon atoms A hydrocarbon group of carbon atoms, or a mixture of several monomers of formula (I), c) 0% to 5% of at least one monomer in the form of acrylamide or methacrylamide or a derivative thereof, such as N- [3 -(Dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamine and mixtures thereof, or at least one water-insoluble monomer, such as acrylic acid Alkyl or alkyl methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl] methacrylate or N- [2- (diamidoamino) ethyl] Esters, vinyls such as vinyl acetate, acetamyl D to 11 each of ketones, styrene, α-methylstyrene and derivatives thereof, or at least one cationic monomer or quaternary ammonium, such as gasification or sulfuric acid [2- (Methacryloxy) ethyl] trimethylammonium, gasified or sulfuric acid [2 -— (propylenemethyleneoxy) ethyl] trimethylammonium, gasified or sulfuric acid [3- (propylenefluorene] Amine) propyl] trimethylammonium, gasified or dimethyldiallylammonium sulfate, chlorinated or sulfuric acid [3-((propylacrylamino) propyl] propyl] trimethylammonium, or at least one Organic fluorinated or organic petrified monomers Molecule is selected from the formula (IIa) or formula (IIb) of formula (Ila) molecule is 122200422311 i11 ”q2 P and represents the number of oxidized dilute units, which is less than or less than 150, and tooth n2 represents the number of oxidized ethylene units, which is less than or equal to, Q1 and y represent at least equal to 1 and such that ≦ (ml + nl + pl ) qi < 15〇 ^ 〇 < (m2 + n2-fp2) q2 < l50 ^ ^ ^ ^-Γ represents a number that makes UK200, I represents a group containing a polymerizable unsaturated functional group, which belongs to the ethylene group Group and propionic acid, tianganqiu @ 夂 methacrylic acid, cis-butenedioic acid, decomposed ubiquitin croton®, and ethyl esters, and urethane unsaturated compounds such as Acrylaminoformate, methacrylamidoformate α α monomethyl-isopropenyl-benzylaminoformate and allylaminoformate group, and substituted or unsubstituted Substituted allyl or vinyl-transformed groups' or groups of ethylenically unsaturated amines or amines,-R4, R5, R1 () and Rn represent hydrogen or methyl or ethyl Rb, R7, R8 and R9 represent a straight or branched alkyl group having 1 to 20 carbon atoms, an aryl group, an alkaryl group or an aralkyl group, or a mixture thereof, -R! 2 represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, -A and B are groups that may exist, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms, and the formula (lib) is 123 200422311 R-A-Si (0B) 3 One of R represents a group containing a polymerizable unsaturated function, which belongs to the vinyl group and acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, croton Group of acids, and vinyl peptides, and urethane unsaturated compounds such as acryl urethane, methacryl urethane, α-α'dimethyl-isopropenyl— Benzylamino and allylamino The group of ethyl formate, and the group of substituted or unsubstituted allyl or vinyl ether 'or the group of women's unsaturated unsaturated amines or amimines, -A is possible Group, in this case, it represents a hydrocarbon group having 1 to 4 carbon atoms,-B represents a hydrocarbon group having 1 to 4 carbon atoms, or a mixture of several of these monomers, d) 0 ° / ◦ To 3% of at least one crosslinking monomer, which is selected from the group consisting of ethylene dimethacrylate, trihydroxypropane triacrylate, allyl acrylate, cis_ Allyl butenoate, methylene_bis_acrylamide, methylene_bis_methacrylamide, tetraallyloxyethane, triallyl cyanurate, polyhydric alcohols such as Groups consisting of neopentyl tetraol, sorbitol, saccharose or other allyl groups or molecules selected from formula (111) ... Where 124 (III) 200422311 -m3, p3, π4 and p4 represent the number of alkylene oxide units, which are less than or equal to 150, -n3 and π4 represent the number of ethylene oxide units, which are less than or equal to 150,-q3 and q4 represent An integer at least equal to 1 such that 0s (m3 + n3 + p3) q3Sl50 and 0s (m4 + n4 + p4) q4si50, -r 'represents a number that makes lsr's200, a R13 represents a polymerizable unsaturated Functional groups belonging to the vinyl group and the group of acrylic acid, methacrylic acid, maleic acid, decomposed aconitic acid, crotonic acid, and ethanoate, and ethyl urethane unsaturated Such as the group of acrylaminocarbamate, methacrylaminocarbamate, α-α-methyl-isopropenyl-benzylaminocarbamate, and allylaminocarbamate, and A group of substituted or unsubstituted allyl or vinyl groups, or a group of dilute unsaturated unsaturated amides or fluorimines,-R14, R15, R20, and R21 represent hydrogen or methyl Or ethyl, and F16, R17, and R19 represent a linear or branched alkyl group having 1 to 20 carbon atoms, Aryl, alkaryl or aralkyl, or mixtures thereof -D and E are groups that may be present, in which case they represent nicotinyl with 1 to 4 carbon atoms, or several of the monomers The mixture becomes a sum of the proportions of a), b), c) and d) equal to 100%. 12. An improved optical brightening agent according to any of the 7th or 8th of the scope of the patent application, characterized in that the copolymer is in its acid form or is monovalent or multivalent neutralized by one or more functional groups The neutralizer is completely or 200422311 neutralized. For example, for monovalent functions, the neutralizer is selected from the group consisting of test cations, especially sodium, oblique, bell, ammonium or -grade, secondary or tertiary fatty slaves. And / or cyclic amines such as stearylamine, ethanolamines (mono, di, and triethanolamine), mono and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, A group consisting of, or, for polyvalent functions, the neutralizing agent is selected from alkaline earth divalent cations, especially magnesium and calcium, or zinc and trivalent cations, including especially ions or certain high-valent cations. Group of people. 13.—A method for dispersing in an aqueous suspension of a mineral substance, characterized by It is to use the common substance according to any one of item i to item 6 of the scope of patent application. '14. A method for dispersing in an aqueous suspension of a mineral substance according to item 13 of the scope of the patent application, characterized in that the copolymer is used in an amount of 0.05% to 5% dry weight relative to the dry weight of the filler and / or pigment, and More particular is the use of the copolymer in an amount of from 01% to 3% dry weight relative to the dry weight of the filler and / or pigment. 15. The method for dispersing in an aqueous suspension of a mineral substance according to any of the 13th or 14th scope of the patent application, characterized in that the mineral substance is selected from the group consisting of calcium carbonate, dolomite, kaolin, talc, gypsum, titanium oxide , Satin white or aluminum hydroxide, mica and mixtures of these fillers, such as talc-carbonate or calcium carbonate-kaolin mixture, or a mixture of calcium carbonate and sodium hydroxide, or a mixture with synthetic or natural fibers, or mineral The common structure of matter, such as talc-calcium carbonate or talc-titanium dioxide, and more particularly is composed of calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof. 126 200422311 16. An aqueous suspension of a mineral substance, characterized in that it contains a copolymer according to any one of the claims 1 to 6 of the scope of the patent application, and more particularly in that it contains relative to fillers and / or pigments 5% to 5% dry weight of the copolymer, and more particularly, it comprises 0.1 to 3% dry weight of the copolymer relative to the filler and / or pigment dry weight. 17. An aqueous suspension of a dispersed mineral substance according to item 16 of the scope of patent application, characterized in that the mineral substance is selected from the group consisting of carbonic acid, dolomite, kaolin, talc, gypsum, titanium oxide, satin white or aluminum hydroxide, Mixtures of mica and these fillers' such as talc-rhenium carbonate or about-kaolin clay mixtures, or mixtures of calcium carbonate and aluminum hydroxide, or mixtures with synthetic or natural fibers, or common structures of minerals, such as talc— Carbonic acid dance or talc-titanium dioxide has a common structure, and more particularly is composed of calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk or a mixture thereof. 18. A method for grinding in an aqueous suspension of a mineral substance, characterized in that a copolymer according to any one of claims 1 to 6 of the scope of patent application is used. 19. The method of grinding in an aqueous suspension of a mineral substance according to item 18 of the scope of application for a patent, characterized in that the copolymer is used in an amount of 0.05 to 5% by dry weight relative to the dry weight of the filler and / or pigment. And, more particularly, in using the copolymer in an amount of from 0.1% to% dry weight relative to the dry weight of the filler and / or pigment. 20. The method of grinding in an aqueous suspension of a mineral substance according to any of the 18th or 19th scope of the patent application, characterized in that the mineral substance is selected from the group consisting of calcium carbonate, dolomite, kaolin, talc, gypsum, and oxidation Titanium, 127 200422311 wrought white or aluminum hydroxide, mixtures of mica and these fillers, such as talc-rhenium carbonate or calcium carbonate-kaolin mixtures, or calcium carbonate and aluminum hydroxide / heart a 'or with synthetic or natural A mixture of fibers, or a common structure of minerals, such as the common structure of talc-calcium carbonate or talc-titanium dioxide, and more particularly is composed of calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof . 21 · —Aqueous suspension of a ground mineral substance, characterized in that it contains a copolymer according to one of the items 1 to 6 of the scope of the patent application, and more particularly that it contains relative to fillers and / or pigments 5% to 5% dry weight of the copolymer, and more particularly uses 1: 1 to 3% dry weight of the copolymer relative to the filler and / or pigment dry weight . 22. An aqueous suspension of a ground mineral substance according to item 21 of the scope of the patent application, characterized in that the mineral substance is selected from the group consisting of calcium carbonate, dolomite, kaolin, talc, gypsum, titanium oxide, and satin White or hydroxide, mixtures of mica and these fillers, such as talc-carbonate or calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate and aluminum hydroxide, or mixtures of synthetic or natural fibers or minerals Such as talc _ calcium carbonate or talc-titanium dioxide common structure, and more particularly contains calcium carbonate such as natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof. 23. A method for manufacturing a filler, characterized in that a copolymer according to any one of claims 1 to 6 of the scope of patent application is used. 24. The method for manufacturing a filler according to item 23 of the scope of patent application, characterized in that the copolymer is used in an amount of 0.05% to 128 200422311 dry weight relative to the dry weight of the filler and / or pigment, and more specifically This is to use the copolymer in an amount of from 0.1% to 1% dry weight relative to the dry weight of the filler and / or pigment. 25 · —a filler, characterized in that it contains a copolymer according to any one of claims 1 to 6 of the scope of the patent application, and more particularly in that it contains a proportion of the total dry weight of the filler and / or pigment 0.05% to 5% dry weight of the copolymer 'and more particularly that it comprises 0.1 to 1% dry weight of the copolymer relative to the total dry weight of the filler and / or pigment. 26. A method for manufacturing a paint coloring material, characterized in that a copolymer according to any one of claims 1 to 6 of the scope of patent application is used. 27. A method for manufacturing a coating colorant according to item 26 of the patent application, 'characterized by using the copolymer in an amount of 5% to 5% by dry weight relative to the dry weight of the filler and / or pigment, and more specifically This is to use the copolymer in an amount of from 0.1% to 2% dry weight relative to the dry weight of the filler and / or pigment. 28 · —a paint colorant, characterized in that it contains a copolymer according to any one of the items 1 to 6 of the scope of patent application, and more particularly in that it contains a total dry matter relative to fillers and / or pigments 5% to 5% dry weight of the copolymer, and more particularly in that it contains 0.1 to 2% dry weight of the copolymer relative to the total dry weight of the filler and / or pigment Thing. 29 · —The use of the copolymer according to any one of items 丨 to 6 of the scope of the patent application as an additive in the suspension of dispersed mineral substances Use of the copolymer of any one of items 6 to 6 as an additive in a suspension of ground mineral matter 129 422311 according to A 3L-manufactured and / or coated paper, characterized in that it contains a copolymer according to any one of claims 1 to 6 of the patent application. 32. A textile composition, characterized in that it comprises a copolymer according to any one of claims 1 to 6 of the patent application. 33. A detergent composition, characterized in that it comprises a copolymer according to any one of claims 1 to 6 of the scope of patent application. 34. A pigment composition characterized in that it contains a copolymer according to any one of claims 1 to 6 of the patent application range. Pick up, 囷 style: (none) 130